US6590041B1 - Chlorinated vinyl chloride-based resin and molded articles - Google Patents

Chlorinated vinyl chloride-based resin and molded articles Download PDF

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Publication number
US6590041B1
US6590041B1 US09/720,515 US72051501A US6590041B1 US 6590041 B1 US6590041 B1 US 6590041B1 US 72051501 A US72051501 A US 72051501A US 6590041 B1 US6590041 B1 US 6590041B1
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Prior art keywords
vinyl chloride
chloride resin
determined
chlorine
cpvc
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Inventor
Yoshihiko Eguchi
Yuhki Gotoh
Hideki Inoue
Kenichi Asahina
Yukio Shibasaki
Yoshiaki Okusako
Yoshinobu Suenaga
Ryo Iijima
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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Priority claimed from JP795599A external-priority patent/JP2000136213A/ja
Priority claimed from JP01317699A external-priority patent/JP4331813B2/ja
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Assigned to SEKISUI CHEMICAL CO., LTD. reassignment SEKISUI CHEMICAL CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ASAHINA, KENICHI, EGUCHI, YOSHIHIKO, GOTOH, YUHKI, IIJIMA, RYO, INOUE, HIDEKI, OKUSAKO, YOSHIAKI, SHIBASAKI, YUKIO, SUENAGA, YOSHINOBU
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms
    • C08F14/06—Vinyl chloride

Definitions

  • the present invention relates to a vinyl chloride resin, a chlorinated vinyl chloride resin and a method of producing the same, a chlorinated vinyl chloride resin pipe, a chlorinated vinyl chloride resin joint and a chlorinated vinyl chloride resin plate.
  • Vinyl chloride resins (hereinafter sometimes referred to also as “PVC” or “PVC resins”) are used in various fields as materials having good mechanical strength, weathering resistance and chemical resistance. Since, however, PVC resins have the drawback of being inferior in shock resistance, various methods have been proposed to improve their shock resistance. Thus, for example, addition of a copolymer having rubber-like properties and/or high-level addition of an inorganic material, a metal powder or the like has been practiced.
  • Japanese Kokoku Publication Sho-44-453 discloses a method comprising blending, with PVC resins, a methyl methacrylate-butadiene-styrene copolymer (MBS copolymer) as a dispersoid.
  • MVS copolymer methyl methacrylate-butadiene-styrene copolymer
  • Japanese Kokai Publication Hei-02-20545 discloses a method comprising blending, with PVC resins, a chlorinated polyethylene (CPE resin) as a dispersoid.
  • PVC resins for providing them with mechanical strength and functions. Therefore, PVC resins highly capable of dispersing other kinds of materials therein and allowing high level addition thereof and having good gelation properties are demanded. Further, since PVC resins excellent in gelation properties are generally excellent in high-speed moldability, PVC resins having good gelation properties as well are desired.
  • the PVC resins be readily disintegrable and have micropores within resin particles with a high void content.
  • chlorinated vinyl chloride resins (hereinafter referred to also as “CPVC” or “CPVC resins”) have been developed which are produced by chlorinating PVC resins and thus improved in heat resistance.
  • CPVC resins While PVC resins have a low thermal deformation temperature and the upper limit temperature allowing their practical use is around 60 to 70° C., hence they cannot be used in contact with hot water, CPVC resins have a thermal deformation temperature higher by 20 to 40° C. as compared with PVC resins, so that they can be used in contact with hot water and are thus favorably used as materials of heat-resistant pipes and heat-resistant joints, typically for hot water supply, or of heat-resistant resin material plates for producing tanks or containers, for instance.
  • CPVC the problem of rusting due to corrosion so far encountered with the conventional metal pipes, metal plates and the like has been liquidated.
  • CPVC resins have a high thermal deformation temperature, a high temperature and great shearing force are required for effecting gelation in the step of molding/fabrication, tending to cause degradation and discoloration of the resins.
  • CPVC resins thus have a narrow margin of moldability and they are often molded into products in an insufficient gelation state and, on such occasions, the products can hardly be said to have fully inherited the performance characteristics intrinsic in the material resins.
  • the pipes and joints for hot water supply are required to have still higher levels of heat resistance and chemical resistance as compared with the conventional pipes and joints for hot water supply. They, in particular, are required to have high shock resistance such that they may withstand water hammer shocks. For that purpose, it is necessary that the gelation of CPVC resins be sufficient.
  • Japanese Kokai Publication Sho-49-6080 discloses a method comprising chlorinating a PVC resin in the form of aggregates consisting of primary particles about 1 ⁇ m in size as resulting from the use of a suspension stabilizer composed of an ionic emulsifier, a water-soluble metal salt and a water-soluble macromolecular dispersant (i.e. proposal for improving resin particles).
  • This method indeed improves the gelation properties in the step of molding/fabrication but, the improvement is not yet satisfactory.
  • a problem arises: a large amount of scale is formed in the step of polymerization and sticks to the polymerizer wall surface to thereby lessen the heat removing effect, hence work is required to remove said scale.
  • Japanese Kkai Publication Hei-04-81446 discloses a method of attaining a high thermal deformation temperature which comprises using a resin composition having a specific chlorine content and a shock resistance enhancer. However, the heat resistance attainable is still below the level intended to reach by us.
  • Japanese Kokai Publication Hei-05-132602 discloses a method of attaining high heat resistance which comprises blending a CPVC resin with a PVC resin so as to obtain a viscosity in a specific range (proposal-for improvement by resin blending)
  • this method is only expected to bring about an improvement in heat resistance by about 3 to 4° C. in terms of Vicat value as well as a certain extent of gelling performance improvement owing to the improvement in melt viscosity.
  • the method can never satisfactorily attain the high levels of heat resistance and gelation properties which are aimed at by us.
  • Japanese Kokai Publication Hei-06-128320 discloses a method of chlorinating PVC-resins which comprises two steps (two-step chlorination method).
  • This method is intended to produce highly heat-resistant CPVC resins by increasing the chlorine content to 70 to 75% by weight (proposal for improvement by high level chlorination).
  • this method can be expected to afford high heat resistance according to the chlorine content, no means is disclosed for preventing the gelation properties from predictably worsening as a result of high level chlorination and, accordingly, the method cannot provide practical levels of high heat resistance and gelation properties.
  • Japanese Kohyo Publication Sho-57-501285 discloses a method of producing highly heat-resistant CPVC resins by effecting the chlorination reaction under ultraviolet irradiation which method employing a chlorine pressure within the range of 25 to 100 psi (1.75 to 7 kg/cm 2 ) and using resin particles restricted in porosity to 0.1 to 0.7 cc/g and in surface area to 0.7 to 2 m 2 /g.
  • a chlorine pressure within the range of 25 to 100 psi (1.75 to 7 kg/cm 2
  • resin particles restricted in porosity to 0.1 to 0.7 cc/g and in surface area to 0.7 to 2 m 2 /g are restricted in porosity to 0.1 to 0.7 cc/g and in surface area to 0.7 to 2 m 2 /g.
  • the ranges given for the porosity and surface area of resin particles are too broad and no preferred ranges are shown therefor.
  • the CPVC resins obtained are thus mostly low in heat resistance.
  • the mean particle diameter and void ratio of a PVC resin in photochlorination under intermittent irradiation are restricted to respective specific ranges.
  • the chlorination reaction within resin particles be made uniform by promoting the diffusion of chlorine in a nonirradiation step.
  • the ready gelation tendency is not aimed at although the heat resistance of the product CPVC resin can be improved.
  • Janpanese Kohyo Publication Sho-57-501184 discloses a method of producing a chlorinated vinyl chloride resin which comprises, in carrying out the chlorination reaction under actinic rays irradiation using liquid chlorine as the main source of chlorine, using, as the PVC resin, a PVC resin occurring as granular resin particles having a mean particle size of 10 to 50 ⁇ m, whose constituent element primary particles have a mean particle size of 0.05 to 5 ⁇ m, and having a porosity of 0.2 to 0.3.
  • the main concerns of this technology are the resin particle size and primary particle size in view of the possibility that the process of chlorine diffusion in the core of each PVC resin particle to be chlorinated might be the rate-determining step in the chlorination reaction of a PVC resin.
  • the CPVC resin obtained shows only a small extent of improvement in heat resistance and in gelation properties. This is because, as reported in “AIChE Journal, October 1988, Vol. 34, No. 10, pages 1683-1690”, the diffusion of chlorine in the chlorination reaction is not determined by an elemental factor called primary particle size or grain size but is presumably governed by the agglomerate size resulting from agglomeration of primary particles.
  • Japanese Kokoku Publication Sho-45-30833 described that when the chlorination is carried out at a temperature of 55 to 80° C. while feeding chlorine with an oxygen concentration of 0.05 to 0.35% by volume at a specified rate, CPVCs having good heat stability can be-obtained. Since, however, the reaction is carried out in the presence of a high concentration of oxygen and at a low temperature, the heat stability is not so markedly high, hence the product cannot tolerate long-time extrusion molding or injection molding.
  • Japanese Kokai Publication Hei-09-328518 proposes a method comprising carrying out the chlorination under ultraviolet irradiation using chlorine having an oxygen concentration of not more than 200 ppm. Since, however, the reaction is carried out at a low temperature by means of ultraviolet irradiation, any CPVC having remarkably good heat stability can not be obtained.
  • Japanese Kokai Publication Hei-09-32822 proposes a method comprising carrying out the chlorination at 110 to 135° C. while feeding chlorine containing 10 to 100 ppm of oxygen. Since the chlorination is carried out at a high temperature in the manner of thermal chlorination, CPVC resins excellent in heat stability can be obtained and the chlorination reaction can proceed smoothly. However, the voids in the interior of particles decrease under the influence of the thermal energy released upon the high temperature reaction, hence sufficient gelation will hardly take place in the step of molding/fabrication. For improving the workability, it is necessary to further cause heat generation from within particles under high temperature and high shearing conditions.
  • high heat resistance vinyl chloride resin moldings improved in heat resistance temperature have advantages over ordinary vinyl chloride resin articles in that they can stand against higher pressures when compared under the same morphological and temperature conditions and in that they can be used at higher temperatures when compared under the same pressure conditions.
  • Japanese Kokai Publication Hei-04-359928 proposes, as heat resistant vinyl chloride resin moldings, heat-resistant and hygienic pipes for hot water supply as produced from a chlorinated vinyl chloride resin (hereinafter referred to as “CPVC”) having a chlorine content of not less than 67.5% by weight as produced by chlorination of a vinyl chloride resin, together with a specific compounding additive.
  • CPVC chlorinated vinyl chloride resin
  • the conventional heat-resistant vinyl chloride resins have a higher viscosity, hence their stress relaxation time is longer, as compared with the ordinary vinyl chloride resins and, therefore, the appearance of the moldings thereof is inferior in smoothness.
  • piping materials for ultra pure water for plant use and like piping materials are required to have a smooth surface with the pipe inside surface unevenness reduced to a minimum so that the propagation of bacteria on the pipe inside surface can be inhibited.
  • Japanese Kokai Publication Hei-09-316267 discloses that piping materials for ultrapure water for plant use having good surface smoothness, while enabling long run production, can be formed by using a composition comprising a chlorinated vinyl chloride resin, organotin stabilizer, oxidized polyethylene wax, modifier, lubricant, processing aid and pigment and so on in specific proportions.
  • SC solvent cracking
  • the invention provides a vinyl chloride resin as well as a chlorinated vinyl chloride resin and a method of producing the same.
  • a chlorinated vinyl chloride resin obtainable by chlorination of a vinyl chloride resin
  • said vinvl chloride resin having a BET specific surface area of 1.3 to 8 m 2 /g and a carbon element-chlorine element 1S bond energy (eV) peak ratio (chlorine element peak ⁇ 2/carbon element peak) of higher than 0.6 as determined by particle surface analysis by ESCA (electron spectroscopy for chemical analysis) (hereinafter referred to as “Invention I-1”).
  • eV carbon element-chlorine element 1S bond energy
  • X is the chlorine content (% by weight) of the chlorinated vinyl chloride resin
  • Y is the amount (g) of methyl alcohol required for initiating precipitation of the chlorinated vinyl chloride resin when 3.0 g of the resin is completely dissolved in 60 g of tetrahydrofuran at 20° C. and then methyl alcohol is gradually added to the solution to thereby cause precipitation of the resin
  • Z is the amount (g) of methyl alcohol required to cause 80% by weight of the resin to precipitate (hereinafter referred to as “Invention I-2”).
  • a chlorinated vinyl chloride resin obtainable by chlorination of a vinyl chloride resin
  • said vinyl chloride resin having a BET specific surface area of 1.3 to 8 m 2 /g and a carbon element-chlorine element 1S bond energy (eV) peak ratio [(chlorine element peak) ⁇ 2/carbon element peak] of higher than 0.6 as determined by particle surface analysis by electron spectroscopy for chemical analysis,
  • agglomerates being obtained by agglomeration of primary particles of the vinyl chloride resin
  • invention I-3 the average particle diameter of the agglomerates being 1 to 7 ⁇ m
  • invention I-4 a heat energy source
  • invention I-5 an average pore size of 0.1 to 0.5 ⁇ m
  • invention I-6 wherein, in the pore volume distribution thereof as determined by mercury porosimetry in the pressure range of 0 to 2,000 kg/cm 2 , the percentage by volume (A1) of voids 0.001 to 0.1 ⁇ m in size to the total volume of voids is 2 to 10% by volume (hereinafter referred to as “Invention I-6”).
  • a chlorinated vinyl chloride resin obtainable by chlorination of a vinyl chloride resin according to Invention I-5 or Invention I-6 (hereinafter referred to as “Invention I-7”).
  • a chlorinated vinyl chloride resin obtainable by chlorination of a vinyl chloride resin, wherein said vinyl chloride resin has a BET specific surface area of 1.3 to 8 m 2 /g, a carbon element-chlorine element 1S bond energy (eV) peak ratio [(chlorine element peak) ⁇ 2/carbon element peak] of higher than 0.6 as determined by particle surface analysis by electron spectroscopy for chemical analysis and a void ratio of 27 to 40% by volume as determined by mercury porosimetry at a pressure of 2,000 kg/cm 2
  • eV carbon element-chlorine element 1S bond energy
  • invention I-8 the percentage by volume (A2) of voids 0.001 to 0.1 ⁇ m in size to the total volume of voids is 2 to 30% by volume (hereinafter referred to as “Invention I-8”)
  • the percentage by volume (A1) of voids 0.001 to 0.1 ⁇ m in size to the total volume of voids is 2 to 10% by volume
  • invention I-9 (hereinafter referred to as “Invention I-9”).
  • a chlorinated vinyl chloride resin according to Invention I-8 or Invention I-9 wherein the percentage by volume (A2) of voids 0.001 to 0.1 ⁇ m in size to the total volume of voids for the chlorinated vinyl chloride resin is 3 to 15% by volume (hereinafter referred to as “Invention I-10”)
  • a chlorinated vinyl chloride resin obtainable by chlorination of a vinyl chloride resin
  • the voids 0.001 to 0.1 ⁇ m in size account for 2 to 15% relative to the total volume of voids (hereinafter referred to as “Invention I-11”).
  • a chlorinated vinyl chloride resin obtainable by chlorination of a vinyl chloride resin
  • invention I-12 BET specific surface area of 2 to 12 m 2 /g
  • a chlorinated vinyl chloride resin obtainable by chlorination of a vinyl chloride resin
  • the voids 0.001 to 0.1 ⁇ m in size account for 2 to 15% relative to the total volume of voids. and the absorbance (cell length 1 cm, measuring temperature 23° C.) of a 1 g/kg tetrahydrofuran solution thereof is not more than 0.8 at the wavelength 235 nm (hereinafter referred to as “Invention I-13”).
  • a chlorinated vinyl chloride resin obtainable by chlorination of a vinyl chloride resin
  • a chlorinated vinyl chloride resin obtainable by chlorination of a vinyl chloride resin and having a chlorine content of 60 to 72% by weight and a void ratio of 30 to 40% by volume as determined by mercury porosimetry at a pressure of 2,000 kg/cm
  • the voids 0.001 to 0.1 ⁇ m in size account for 2 to 15% relative to the total volume of voids
  • a chlorinated vinyl chloride resin obtainable by chlorination of a vinyl chloride resin
  • a chlorinated vinyl chloride resin obtainable by chlorination of a vinyl chloride resin
  • the voids 0.001 to 0.1 ⁇ m in size account for 2 to 15% relative to the total volume of voids
  • X is the chlorine content (% by weight) of the chlorinated vinyl chloride resin and Y is the amount (g) of methyl alcohol required for initiating precipitation of the chlorinated vinyl chloride resin when 3.0 g of the resin is completely dissolved in 60 g of tetrahydrofuran and then methyl alcohol is gradually added to the solution to thereby cause precipitation of the resin, and Z is the amount (g) of methyl alcohol required to cause 80% by weight of the resin to precipitate (hereinafter referred to as “Invention I-17”).
  • a chlorinated vinyl chloride resin obtainable by chlorination of a vinyl chloride resin
  • Y is the amount (g) of methyl alcohol required for initiating precipitation of the chlorinated vinyl chloride resin when 3.0 g of the resin is completely dissolved in 60 g of tetrahydrofuran at 20° C. and then methyl alcohol is gradually added to the solution to thereby cause precipitation of the resin
  • Z is the amount (g) of methyl alcohol required to cause 80% by weight of the chlorinated vinyl chloride resin to precipitate (hereinafter referred to as “Invention I-18”).
  • vinyl chloride resin has a BET specific surface area of 1.3 to 8 m 2 /g and a carbon element-chlorine element 1S bond energy (eV) peak ratio (chlorine element peak ⁇ 2/carbon element peak) of higher than 0.6 as determined by particle surface analysis by ESCA (electron spectroscopy for chemical analysis)
  • invention I-20 wherein the vinyl chloride resin has a BET specific surface area of 1.5 to 5 m 2 /g.
  • a chlorinated vinyl chloride resin obtainable by chlorination of a vinyl chloride resin and having a chlorine content of 72 to 76% by weight and a void ratio of 30 to 40% by volume as determined by mercury porosimetry at a pressure of 2,000 kg/cm 2
  • a chlorinated vinyl chloride resin obtainable by chlorination of a vinyl chloride resin and having a chlorine content of 72 to 76% by weight, a void ratio of 30 to 40% by volume as determined by mercury porosimetry at a pressure of 2,000 kg/cm 2 and a BET specific surface area of 2 to 12 m 2 /g (hereinafter referred to as “Invention II-2”).
  • invention II-3 having a carbon element-chlorine element 1S bond energy (eV) peak ratio (chlorine element peak ⁇ 2/carbon element peak) of higher than 0.6 as determined by particle surface analysis by ESCA (electron spectroscopy for chemical analysis) (hereinafter referred to as “Invention II-3”).
  • eV carbon element-chlorine element 1S bond energy
  • vinyl chloride resin has a BET specific surface area of 1.3 to 8 m 2 /g and a carbon element-chlorine element 1S bond energy (eV) peak ratio (chlorine element peak/carbon element peak) of higher than 0.6 as determined by particle surface analysis by ESCA (electron spectroscopy for chemical analysis)
  • invention II-4 a chlorine content of 72 to 76% by weight by introducing liquid chlorine or gaseous chlorine into a reaction vessel containing the vinyl chloride resin in a state suspended in an aqueous medium at a temperature within the range of 70 to 135° C.
  • a chlorinated vinyl chloride resin pipe having a Vicat softening temperature of not lower than 145° C. as determined under a load of 1 kgf by the method according to JIS K 7206 (hereinafter referred to as “Invention III-1”).
  • a chlorinated vinyl chloride resin pipe having a Vicat softening temperature of not lower than 155° C. as determined under a load of 1 kgf by the method according to JIS K 7206 (hereinafter referred to as “Invention III-2”).
  • a chlorinated vinyl chloride resin pipe having avicat softening temperature of not lower than 170° C. as determined under a load of 1 kgf by the method according to Jis K 7206 (hereinafter referred to as “Invention III-3”).
  • a chlorinated vinyl chloride resin pipe having a Vicat softening temperature of not lower than 145° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111 (hereinafter referred to as “Invention III-4”).
  • a chlorinated vinyl chloride resin pipe having a Vicat softening temperature of not lower than 155° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111 (hereinafter referred to as “Invention III-5”).
  • a chlorinated vinyl chloride resin pipe having a Vicat softening temperature of not lower than 170° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111 (hereinafter referred to as “Invention III-6”).
  • a chlorinated vinyl chloride resin pipe having a Vicat softening temperature of not lower than 155° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 20 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111 (hereinafter referred to as “Invention III-8”).
  • a chlorinated vinyl chloride resin pipe having a Vicat softening temperature of not lower than 170° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 20 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111 (hereinafter referred to as “Invention III-9”).
  • a chlorinated vinyl chloride resin joint having a Vicat softening temperature of not lower than 145° C. as determined under a load of 1 kgf by the method according to JIS K 7206 (hereinafter referred to as “Invention III-10”)
  • a chlorinated vinyl chloride resin joint having a Vicat'softening temperature of not lower than 155° C. as determined under a load of 1 kgf by the method according to JIS K 7206 (hereinafter referred to as “Invention III-11”).
  • a chlorinated vinyl chloride resin joint having a Vicat softening temperature of not lower than 170° C. as determined under a load of 1 kgf by the method according to JIS K 7206 (hereinafter referred to as “Invention III-12”).
  • a chlorinated vinyl chloride resin joint having a Vicat softening temperature of not lower than 145° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111 (hereinafter referred to as “Invention III-13”).
  • a chlorinated vinyl chloride resin joint having a Vicat softening temperature not lower than 155° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111 (hereinafter referred to as “Invention III-14”).
  • a chlorinated vinyl chloride resin joint having a Vicat softening temperature of not lower than 170° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111 (hereinafter referred to as “Invention III-15”).
  • a chlorinated vinyl chloride resin joint having a Vicat softening temperature of not lower than 145° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 20 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111 (hereinafter referred to as “Invention III-16”).
  • a chlorinated vinyl chloride resin joint having a Vicat softening temperature of not lower than 155° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 20 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111 (hereinafter referred to as “Invention III-17”).
  • a chlorinated vinyl chloride resin joint having a Vicat softening temperature of not lower than 170° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 20 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111 (hereinafter referred to as “Invention III-18”).
  • a chlorinated vinyl chloride resin plate having a Vicat softening temperature of not lower than 145° C. as determined under a load of 1 kgf by the method according to JIS K 7206 (hereinafter referred to as “Invention III-19”)
  • a chlorinated vinyl chloride resin plate having a Vicat softening temperature of not lower than 155° C. as determined under a load of 1 kgf by the method according to JIS K 7206 (hereinafter referred to as “Invention III-20”).
  • a chlorinated vinyl chloride resin plate having a Vicat softening temperature of not lower than 170° C. as determined under a load of 1 kgf by the method according to JIS K 7206 (hereinafter referred to as “Invention III-21”).
  • a chlorinated vinyl chloride resin plate having a Vicat softening temperature of not lower than 155° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111 (hereinafter referred to as “Invention III-23”).
  • the invention provides a heat-resistant vinyl chloride resin molding and a heat-resistant vinyl chloride resin pipe.
  • a heat-resistant vinyl chloride resin molding having a heat resistance temperature of not lower than 125° C. and a surface roughness Rmax of not more than 0.5 ⁇ m (hereinafter referred to as “Invention IV-1”).
  • invention IV-2 having a decomposition time of not shorter than 30 minutes as determined in an oven at 200° C.
  • invention. IV-3 having a heat resistance temperature of not lower than 125° C. and a surface roughness Rmax of not more than 0.5 ⁇ m
  • invention IV-4 having a decomposition time of not shorter than 30 minutes as determined in an oven at 200° C.
  • a heat-resistant vinyl chloride resin pipe obtainable by molding a heat-resistant vinyl chloride resin
  • said heat-resistant vinyl chloride resin being obtained by chlorination of a vinyl chloride resin having a viscosity average degree of polymerization of 900 to 1,100 to a chlorine content of 66.0 to 67.5% by weight (hereinafter referred to as “Invention IV-5”).
  • a heat-resistant vinyl chloride resin pipe according to Invention IV-3, Invention IV-4 or Invention IV-5 which is to serve as a piping material for pure water distribution (hereinafter referred to as “Invention IV-6”).
  • chlorine content and “degree of chlorination” are to be construed as synonymous
  • PVC polyvinyl chloride resin
  • CPVC CPVC resin
  • chlorinated vinyl chloride resin are to be construed as synonymous.
  • the expression “60-772% by weight”, when used with respect to the chlorine content, means “not less than 60% by weight but less than 72% by weight”.
  • the present invention provides a chlorinated vinyl chloride resin having good gelation properties and heat resistance by paying due attention to the surface condition and interior condition of vinyl chloride particles and further to the distribution of chlorination in the chlorinated vinyl chloride resin to be obtained.
  • the PVC resin of the invention is a resin produced by polymerizing, by a method known in the art, monomeric vinyl chlorine alone or a mixture of monomeric vinyl chloride and another or other monomers copolymerizable with monomeric vinyl chloride.
  • the other monomers copolymerizable with monomeric vinyl chloride are not particularly restricted but include, among others, alkyl vinyl esters such as vinyl acetate; ⁇ -monoolefins such as ethylene and propylene; vinylidene chloride; styrene and the like. These may be used singly or two or more of them may be used in combination.
  • the average degree of polymerization of the above PVC resin is not critical but may be within the conventional range of 400 to 3,000.
  • the PVC resin of the invention has a BET specific surface area of 1.3 to 8 m 2 /g. When it is less than 1.3 m 2 /g, the number of micropores not greater than 0.1 ⁇ m in the interior of PVC resin particles is not sufficient for the chlorination to proceed uniformly in the step of chlorination, so that the heat resistance of the product CPVC resin is not improved. When it is in excess of 8 m 2 /g, the heat resistance of PVC resin particles themselves decreases. Hence, the above range is critical, and 2 to 6 m 2 /g is preferred.
  • the carbon element-chlorine element IS bond energy (eV) peak ratio [(chlorine element peak) ⁇ 2/carbon element peak] as found in particle surface analysis by electron spectroscopy for chemical analysis (ESCA) of the PVC resin of the invention is in excess of 0.6.
  • eV carbon element-chlorine element IS bond energy
  • the ready gelling properties of the PVC resin itself may be impaired and/or problems may arise with respect to the moldability/fabricability of the product CPVC resin, presumably due to adsorption of a dispersant and/or like additive on the surface of PVC resin particles.
  • the rate of chlorination becomes slow at the late stage of chlorination.
  • the above range is thus critical. Preferably, it is above 0.7.
  • PVC resins the above-defined peak ratio of which is above 0.6
  • skin PVC resin small in outer covering
  • a skinless PVC resin PVC resin small in outer covering
  • a skinless PVC resin is preferably used.
  • the peak ratio value of 0 means that the surface of vinyl chloride resin particles is covered with some chlorine-free substance other than a vinyl chloride resin
  • the peak ratio value of 1 means that the surface of PVC resin particles is wholly covered with vinyl chloride components alone.
  • the PVC resin of the invention has a void ratio of 27 to 40% by volume relative to the volume of PVC resin particles as determined by mercury porosimetry at a pressure of 2,000 kg/cm 2 .
  • a void ratio of 27 to 40% by volume relative to the volume of PVC resin particles as determined by mercury porosimetry at a pressure of 2,000 kg/cm 2 .
  • chlorine cannot diffuse into resin voids to a sufficient extent during the chlorination reaction, hence the chlorination degree distribution becomes excessive, resulting in poor moldability/fabricability.
  • the void ratio is thus restricted to the above range and preferably is 30 to 37% by volume.
  • the PVC resin of the invention has an average pore size of 0.1 to. 0.5 ⁇ m.
  • it is less than 0.1 ⁇ m, gaps are too narrow to achieve the desired improvement in high-level filling of inorganic materials, for instance, and, in the chlorination reaction, the gaps will not effectively serve in the chlorination reaction, namely chlorine cannot diffuse to a sufficient extent but the chlorination distribution within resin particles becomes excessively uneven, with the result that the CPVC obtained has poor heat resistance and a prolonged time is required for the chlorination reaction.
  • it is in excess of 0.5 ⁇ m the dispersibility of inorganic materials, among others, cannot be improved. Further, in the chlorination reaction, chlorine cannot diffuse throughout PVC resin particles but the chlorination distribution within resin particles becomes excessively uneven, hence the CPVC resin obtained has poor heat resistance.
  • the average pore size referred to above is a numerical value to be measured for more quantitatively defining the voids in PVC resin particles. It can be measured by mercury porosimetry within the pressure range of 0 to 2,000 kg/cm 2 . Since the void pore size in resin particles is a function of the pressure of mercury for filling void pores with the resin, the volume distribution of void pore sizes can be measured by continuously measuring the filling pressure and mercury weight. The average pore size in question can be calculated from the void pore size distribution measured in that manner.
  • the volume percentage (A1) of voids 0.001 to 0.1 ⁇ m in size relative to the total void volume in the pore volume distribution measured by mercury porosimetry within the pressure range of 0 to 2,000 kg/cm 2 is preferably 2 to 10% by volume, although it is not particularly restricted.
  • the void volume percentage (A1) for the range of 0.001 to 0.1 ⁇ m is less than 2% by volume based on the total void volume, the proportion of microporous voids which resin particles have becomes decreased and the diffusion of chlorine may not be effected in a balanced manner in some instances.
  • the diffusion of chlorine into those regions in the interior of resin particles where the void pore size is small may not proceed smoothly and the chlorination degree distribution within resin particles may become too large accordingly.
  • it is in excess of 10% by volume the diffusion of chlorine into those regions in the interior of particles where the void pore size is small may proceed excessively, the chlorine supply itself cannot catch up with the diffusion and, as a result, the chlorination degree distribution within resin particles may become excessive, too.
  • a more preferred range is 3 to 7% by volume.
  • the PVC resin of the invention can be obtained, for example, by suspension polymerization in an aqueous medium containing partially saponified polyvinyl acetate with a high saponification degree (60 to 90 mole percent) or low saponification degree (20 to 60 mole percent), or both, a higher fatty acid ester or the like as the dispersant, and an anionic emulsifier, a nonionic emulsifier or the like as the emulsifier.
  • the polymerizer (pressure-resistantautoclave) which can be used in producing the above PVC resin by polymerization is not particularly restricted in shape and structure but may be any of those conventionally used in PVC resin polymerization, for instance.
  • the agitating blades are not particularly restricted but include those in general use, such as Pfaudler blades, paddle blades, turbine blades, fan turbine blades and bull margin blades, among others. Pfaudler blades are judiciously used, however, and the combined use of baffle plates is not particularly restricted.
  • the PVC resin of the invention can give CPVC resins excellent in gelation properties and heat resistance.
  • the chlorinated vinyl chloride resin of Invention I-2 preferably satisfies the following relations (1) and (2):
  • X is the chlorine content (% by weight) of the chlorinated vinyl chloride resin
  • Y is the amount (g) of methyl alcohol required for initiating precipitation of the chlorinated vinyl chloride resin when 3.0 g of the resin is completely dissolved in 60 g of tetrahydrofuran at 20° C. and then methyl alcohol is gradually added to the solution to thereby cause precipitation of the resin
  • Z is the amount (g) of methyl alcohol required to cause 80% by weight of the resin to precipitate.
  • Y amount of methyl alcohol required for initiating precipitation of the chlorinated vinyl chloride resin
  • Z total amount of methyl alcohol required to cause 80% by weight of the chlorinated vinyl chloride resin to precipitate
  • the chlorinated vinyl chloride resin satisfying the above relations (1) and (2) has excellent gelation properties, namely good workability, and high heat resistance.
  • the average diameter of agglomerates each resulting from agglomeration of primary particles of the vinyl chloride resin is 1 to 7 ⁇ m.
  • the scale adhesion to the polymerizer wall increases and produces an increased amount of a finer resin powder fraction in the step of chlorinated vinyl chloride resin production, causing troubles in handling.
  • it is greater than 7 ⁇ m the diffusion of chlorine in the step of chlorination suddenly slows down and the diffusion becomes a rate-determining step for the chlorination reaction, so that the chlorination degree distribution becomes too broad and the chlorinated vinyl chloride resin obtained can no more be expected to have an improved level of heat resistance.
  • much energy is required for disintegrating agglomerate particles, hence the gelation properties of the chlorinated vinyl chloride resin cannot be improved.
  • the above range is thus critical.
  • a preferred range is 1.5 to 5 ⁇ m.
  • the agglomerate diameter can be measured by observation under a commercial transmission electron microscope and photography, for instance.
  • vinyl chloride resin particles have similar hierarchic structures (“Polyvinyl Chloride Resins —Fundamentals and Applications”, pages 214-218, edited by Kinki Chemical Society Vinyl Section, published 1988 by Nikkan Kogyo Shimbunsha)
  • the above agglomerates belong to the above hierarchic structures and each is a mass of primary particles collected together by weak bonding.
  • the vinyl chloride resin having the above-mentioned BET specific surface area, IS bond energy (eV) peak ratio and average agglomerate diameter can be obtained, for example by suspension polymerization in an aqueous medium containing high saponification degree (60 to 90 mole percent) polyvinyl acetate or low saponification degree (20 to 60 mole percent) polyvinyl acetate, or both, a higher fatty acid ester or the like as the dispersant, and an anionic emulsifier, nonionic emulsifier or the like as the emulsifier.
  • the PVC resin to be used in the production of the CPVC resin according to.Invention I-6 has a BET specific surface area of 1.3 to 8 m 2 /g, a carbon element-chlorine element 1S bond energy (eV) peak ratio [(chlorine element peak) ⁇ 2/carbon element peak] of higher than 0.6 as determined by particle surface analysis by electron spectroscopy for chemical analysis and a void ratio of 27 to 40% by volume as determined by mercury porosimetry at the pressure 2,000 kg/cm 2 . Suited for use as such PVC resin is the PVC resin according to Invention I-5.
  • eV carbon element-chlorine element 1S bond energy
  • the CPVC resin according to Invention I-6 is produced by chlorinating the above PVC resin.
  • the percentage by volume (A2) of voids 0.001 to 0.1 gm in size to the total volume of voids of the CPVC resin is 2 to 30% by volume in the pore volume distribution determined by mercury porosimetry in the pressure range of 0 to 2,000 kg/cm 2 .
  • it is less than 5% by volume, the frictional heat generation by shearing in the interior of particles takes place with difficulty, hence the gelation state in the step of molding is insufficient.
  • it is in excess of 30% violent local heat generation occurs and unfavorably causes decomposition in the step of molding.
  • it is 10 to 25% by volume, more preferably 3 to 15% by volume.
  • the percentage of voids 0.001 to 0.1 ⁇ m in size (A2) of the above CPVC resin and the percentage of voids 0.001 to 0.1 ⁇ m in size (A1) of the PVC resin satisfy the following relation (1):
  • the method of chlorinating the PVC resin used in accordance with the invention is not particularly restricted. It is necessary, however, to maintain the porosity and high void content of the PVC resin and, therefore, the chlorination is preferably effected by contacting chlorine with the above PVC resin in a suspended state. In carrying out the chlorination in a suspended state, it is also possible to effect the chlorination by blowing chlorine directly into the very suspension, without separating the PVC resin obtained by suspension polymerization from the aqueous medium.
  • the above chlorination in a suspended state can be carried out, for example, in the manner of photochemical chlorination by irradiating the reaction product with light, or can be carried out by exciting resin bonds and/or chlorine by heating.
  • the source of light for causing chlorination by light energy is not particularly restricted but mention may be made of ultraviolet rays, and visible light from a mercury vapor lamp, arc lamp, incandescent lamp, fluorescent lamp or carbon arc, for instance. In particular, ultraviolet rays are effective.
  • the method of heating for causing chlorination by thermal energy is not particularly restricted but mention may be made of exterior jacket heating through the reactor wall, internal jacket heating and heating by blowing steam into the reactor, among others. Generally, the exterior jacket system or internal jacket system is effective.
  • the one comprising resin bond and/or chlorine excitation by thermal energy to thereby promote the chlorination is preferred.
  • the reason is as follows.
  • the matters of special concern in the present invention are the void ratio and pore distribution of the resin particles, in particular the distribution of voids occurring within the particles in a three-dimensional hierarchic manner.
  • thermal energy acts uniformly to the inside of particles
  • light irradiation energy acts only on the surface of resin particles, with the result that the chlorination reaction necessarily proceeds predominantly on the surface of resin particles. Therefore, for realizing the chlorination reaction uniformly with respect to both diffusion and reaction, it is preferably to carry out the chlorination reaction by utilizing thermal energy.
  • the reaction is preferably carried out at 70 to 135° C.
  • the hierarchic structure of the interior of particles swells and softens and pores are filled up at the early stage of reaction and, therefore, the resin after chlorination will have poor moldability/fabricability.
  • the rate of reaction becomes slow.
  • a more preferred temperature is within the range of 90 to 125° C.
  • the aqueous medium to be used in the above chlorination in a suspended state may contain a small amount of a ketone such as acetone or methyl ethyl ketone and further, necessary, a small amount of a chlorine-containing solvent such as hydrochloric acid, trichloroethylene and carbon tetrachloride may be added.
  • a ketone such as acetone or methyl ethyl ketone
  • a chlorine-containing solvent such as hydrochloric acid, trichloroethylene and carbon tetrachloride
  • the chlorine content of the product CPVC resin is preferably adjusted to 60 to 72% by weight.
  • the PVC resin of the invention and the CPVC resin of the invention can be hot-blended or cold-blended with appropriate amounts of additives such as an shock resistance improver, heat stabilizer, auxiliary stabilizer, lubricant, processing aid, filler, pigment, plasticizer and/or the like, using a Henschel mixer, ribbon mixer or Banbury mixer, for instance.
  • additives such as an shock resistance improver, heat stabilizer, auxiliary stabilizer, lubricant, processing aid, filler, pigment, plasticizer and/or the like, using a Henschel mixer, ribbon mixer or Banbury mixer, for instance.
  • the above shock resistance improver is not particularly restricted but may be any of those known in the art.
  • a copolymer having rubber-like properties are suited for use.
  • the copolymer having rubber-like properties is not particularly restricted but includes, among others, ethylene-vinyl acetate copolymers (EVA), chlorinated polyethylene (CPE), acrylonitrile-butadiene-styrene copolymers (ABS), methyl methacrylate-butadiene-styrene copolymers (MBS), ethylene-propylene copolymers (EPR), ethylene-propylene-diene monomer copolymers (EPDM) and acrylonitrile-butadiene copolymers (NBR).
  • EVA ethylene-vinyl acetate copolymers
  • CPE chlorinated polyethylene
  • ABS acrylonitrile-butadiene-styrene copolymers
  • MVS methyl methacrylate-butadiene-
  • MVS methyl methacrylate-butadiene-styrene copolymers
  • CPE chlorinated polyethylene
  • the above shock resistance improver is used at an addition amount appropriately selected according to the required level of shock resistance.
  • it is used in an amount of 1 to 70 parts by weight, more preferably 2 to 35 parts by weight, per 100 parts by weight of the PVC resin of the invention or the CPVC resin of the invention.
  • the above heat stabilizer is not particularly restricted but includes, among others, organotin compounds such as dimethyltin mercaptides, dibutyltin mercaptides, dibutyltin maleate, dibutyltin maleate polymer, dioctyltin maleate, dioctyltin maleate polymer, dibutyltin laurate and dibutyltin laurate polymer; lead compounds such as lead stearate, dibasic lead phosphite and tribasic lead sulfate; calcium-zinc stabilizers, barium-zinc stabilizers and barium-cadmium stabilizers.
  • organotin compounds such as dimethyltin mercaptides, dibutyltin mercaptides, dibutyltin maleate, dibutyltin maleate polymer, dioctyltin maleate, dioctyltin maleate polymer, dibutyltin laurate and di
  • auxiliary stabilizer is not particularly restricted but includes, among others, epoxi-dized soybean oil, epoxidized linseed oil, epoxidized tetrahydrophthalate, epoxidized polybutadiene and phosphate esters.
  • the above lubricant is not particularly restricted but includes, among others, montanic acid wax, paraffin wax, polyethylene wax, stearic acid, stearyl alcohol and butyl stearate.
  • the above processing aid is not particularly restricted but includes, among others, acrylic processing aids, which are alkyl acrylate/alkyl methacrylate copolymers having a weigh average molecular weight of 100,000 to 2,000,000, for example n-butyl acrylate/methyl methacrylate copolymers and 2-ethylhexyl acrylate/methyl methacrylate/butyl methacrylate copolymers.
  • acrylic processing aids which are alkyl acrylate/alkyl methacrylate copolymers having a weigh average molecular weight of 100,000 to 2,000,000, for example n-butyl acrylate/methyl methacrylate copolymers and 2-ethylhexyl acrylate/methyl methacrylate/butyl methacrylate copolymers.
  • the above filler is not particularly restricted but includes, among others, calcium carbonate and talc.
  • the above pigment is not particularly restricted but includes, among others, organic pigments such as azo, phthalocyanine and threne pigments and dye lakes; and inorganic pigments such as oxide type, molybdenum chromate type, sulfides-selenide type, and ferrocyanide type.
  • organic pigments such as azo, phthalocyanine and threne pigments and dye lakes
  • inorganic pigments such as oxide type, molybdenum chromate type, sulfides-selenide type, and ferrocyanide type.
  • the above plasticizer is added for improving the moldability/fabricability.
  • the plasticizer is not particularly restricted but includes, among others, dibutyl phthalate, di-2-ethylhexyl phthalate and di-2-ethylhexyl adipate.
  • the resin composition obtained by compounding the PVC resin of the invention or the CPVC resin of the invention with various ingredients can be molded by any of the conventional molding methods, for example by extrusion molding, calender molding, contour molding or press molding, to give moldings.
  • the present inventors found that the voids, too, can have a hierarchic structure.
  • the hierarchic structure of the voids was found markedly when the BET specific surface area is within the range of 1.3 to 8 m 2 /g and the peak ratio found by ESCA is in excess of 0.6. Based on this finding, it was found that a specific void ratio range and a specific average pore size range are best suited.
  • those CPVC resins obtained by chlorinating such a PVC resin show good characteristics when evaluated for heat resistance (Vicat softening temperature), workability (gelling temperature) and heat stability and, therefore, the chlorination degree distribution is within a preferred range.
  • the present invention presents those structural factors of a PVC resin which make it possible for chlorine to diffuse neither excessively nor insufficiently from the circumference to the central part of particles in the chlorination reaction.
  • the CPVC resin of the invention is intended to be improved in heat resistance by chlorination of a PVC resin and, at the same time, is intended to be improved in moldability/fabricability by causing both the PVC resin and the CPVC resin obtained after chlorination to have particular intraparticle structure characteristics. Furthermore, it was found that when the void volume (A1) of pores having a pore size of 0.001 to 0.1 ⁇ m in the pore distribution of the PVC resin is within the range of 2 to 10% by volume, the pore volume in the pore distribution range of 0.001 to 0.1 ⁇ m in pore size is more increased. This finding has now led to completion of Invention I-8. This noteworthy phenomenon is presumably related with the specific surface area of the PVC resin and the particle structure specified by ESCA.
  • the PVC to be used in the production of the CPVC of the invention is preferably the PVC obtained by the production method described in Japanese Kokai Publication Hei-08-120007, Japanese Kokai Publication Hei-08-295701, Japanese Kokai Publication Hei-09-132612 or Japanese Kokai Publication Hei-09-227607.
  • the present invention is defined by a chlorine content, a void ratio and a void volume for pores of 0.001 to 0.1 ⁇ m, each specified above.
  • the CPVC of the invention has a chlorine content of 60 to 72% by weight.
  • the expression “60 to 72% by weight” means that the content is not less than 60% by weight but less than 72% by weight.
  • the chlorine content is less than 60% by weight, the improvement in heat resistanceis unsatisfactory.
  • it is 72% by weight or above, the molding becomes difficult and the gelation becomes insufficient.
  • a preferred range is 63 to 70% by weight.
  • the CPVC of the invention has a void ratio of 30 to 40% by volume.
  • the void ratio is the one measured by mercury porosimetry at the pressure 2,000 kg/cm 2 .
  • the void ratio is less than 30%, the gelation is retarded in the step of molding, which is undesirable from the moidability/fabricability viewpoint.
  • it exceeds 40% by volume the biting by the screw becomes insufficient and poor gelation results.
  • a preferred range is 31 to 38% by volume.
  • the void volume for pores of 0.001 to 0.1 ⁇ m in the pore volume distribution determined by mercury porosimetry in the pressure range of 0 to 2,000 kg/cm 2 is 2 to 15% by volume relative to the total void volume.
  • the void pore size in resin particles is a function of the pressure of mercury filled into void pores of the resin. Therefore, the pore size distribution can be determined by continuously measuring the filling pressure and mercury weight.
  • the void volume for the range 0.001 to 0.1 ⁇ m is less than 2% by volume relative to the total void volume, the proportion of micropores in the interior of particles is insufficient, hence the product is inferior in gelation propety in the step of molding.
  • a preferred void volume for the range 0.001 to 0.1 ⁇ m is 3 to 13% by volume relative to the total void volume.
  • Invention I-12 is defined by a chlorine content, a void ratio and a BET specific surface area, each specified.
  • the CPVC of Invention I-12 has a BET specific surface area of 2 to 12 m 2 /g.
  • the BET specific surface area is less than 2 m 2 /g, the proportion of micropores in the interior of particles is insufficient, so that intraparticle melting becomes difficult to occur in the step of molding, hence the gelation performance gets worse.
  • the BET specific surface area is above 12 m 2 /g, the generation of heat of friction from the inside occurs rapidly and the heat stability in the step of molding becomes decreased.
  • a preferred BET specifics surface area is 3 to 10 m 2 /g.
  • Invention I-13 is defined by a chlorine content, a void ratio, a void volume for 0.001 to 0.1 ⁇ m and an absorbance at 235 nm, each specified.
  • the chlorine content, void ratio and void volume for 0.001 to 0.1 ⁇ m of the CPVC according to Invention I-13 are the same as those according to Invention I-11.
  • the absorbance (cell length 1 cm, measuring temperature 23° C.) of a 1 g/kg tetrahydrofuran solution of the CPVC according to Invention I-13 is not more than 0.8 at the wavelength 235 nm.
  • the absorbance value is used for quantitating exotic structures in the molecular chain resulting from the chlorination reaction and is used as an indicator of heat stability.
  • the absorbance is determined by measuring the ultraviolet absorption spectrum and reading the absorbance value at the wavelength 235 nm (cell length 1 cm, measuring temperature 23° C.) at which radiant energy is absorbed by the exotic structures —CH ⁇ CH—C( ⁇ O)— and —CH ⁇ CH—CH ⁇ CH— occurring in the CPVC.
  • the reason why the absorbance should be not more than 0.8 is as follows.
  • the chlorine atom bound to the carbon atom adjacent to the double bond is unstable and hydrogen chloride elimination occurs from that site, thus, with the increase in absorbance value, the hydrogen chloride elimination becomes more and more ready to occur, hence the heat stability decreases.
  • the absorbance value exceeds 0.8 the influence of the exotic structures in the molecular chain increases, with the result that the heat stability becomes poor.
  • a preferred value is not more than 0.2.
  • the method of chlorination by which the above-defined absorbance of the 1 g/kg tetrahydrofuran solution can be maintained at 0 to 0.8 is not particularly restricted but includes the thermal chlorination and photochlorination techniques, preferably the high temperature chlorination technique.
  • the high heat stability obtainable by carrying out the reaction at a high temperature is attributable to the fact that the oxidation (formation of exotic structures, typically the carbonyl group) during the chlorination reaction becomes difficult to occur as the temperature rises (as the temperature rises, the reaction equilibrium shifts in the direction to suppression of their formation).
  • the reaction is carried out at a temperature within the range of 70 to 135° C., more preferably within the range of 90 to 125° C.
  • the rate of the chlorination reaction is low and it becomes necessary to add a large amount of a reaction catalyst, typically a peroxide, for causing the reaction to proceed.
  • a reaction catalyst typically a peroxide
  • the resin obtained is inferior in heat stability.
  • the reaction temperature is lower than 70° C.
  • chlorine is readily soluble in water and oxygen is readily generated in the reaction vessel.
  • the resin obtained shows inferior heat stability.
  • the resin is deteriorated by thermal energy and the CPVC obtained shows discoloration.
  • the CPVC according to Invention I-14 is defined by a chlorine content, a void ratio, a BET specific surface area and an absorbance at 235 nm, each specified.
  • the chlorine content, void ratio and BET specific surface area are the same as those according to Invention I-2, and the absorbance at 235 nm is the same as that according to Invention I-13.
  • the CPVC according to Invention I-15 is defined by a chlorine content, a void ratio, a void volume for 0.001 to 0.1 ⁇ m and an absorbance at 235 nm, each specified.
  • the chlorine content, void ratio and void volume for 0.001 to 0.1 ⁇ m are the same as those according to Invention I-13.
  • the absorbance at 235 nm of the CPVC according to Invention I-15 is not more than 0.2.
  • the absorbance at 235 nm is not more than 0.2, the CPVC shows particularly good heat stability.
  • the CPVC according to Invention I-16 is defined by a chlorine content, a void ratio, a BET specific surface area and an absorbance at 235 nm, each specified.
  • the chlorine content, void ratio and BET specific surface area are the same as those according to Invention I-14, and the absorbance at 235 nm is the same as that according to Invention I-15.
  • the CPVCs according to Invention I-11 to Invention I-18 can be produced, for example, by using the method of producing a chlorinated vinyl chloride resin according to the invention (Invention I-19 to Invention 1-21).
  • X is the chlorine content (% by weight) of the chlorinated vinyl chloride resin
  • Y is the amount (g) of methyl alcohol required for initiating precipitation of the chlorinated vinyl chloride resin when 3.0 g of the resin is completely dissolved in 60 g of tetrahydrofuran at 20° C. and then methyl alcohol is gradually added to the solution to thereby cause precipitation of the resin
  • Z is the amount (g) of methyl alcohol required to cause 80% by weight of the resin to precipitate.
  • Y amount of methyl alcohol required for initiating precipitation of the chlorinated vinyl chloride resin
  • Z amount of methyl alcohol required to cause 80% by weight of the chlorinated vinyl chloride resin to precipitate
  • the CPVC satisfying the above relations (1) and (2) is narrow in chlorination degree distribution (uniformly chlorinated until the core of particles) and has high heat resistance.
  • the method comprising carrying out the heat chlorination reaction at a high temperature.
  • the reason why uniform chlorination within particles can be attained by the high temperature reaction is that the rate of diffusion is a function of temperature and the diffusion of chlorine into the interior of particles readily occurs at elevated temperatures.
  • the chlorination reaction is carried out at a temperature within the range of 120 to 135° C.
  • the diffusion of chlorine into the interior of particles is not sufficient, hence the above relations (1) and (2) cannot be satisfied.
  • the chlorination degree distribution in the interior of particles is broad and, as a result, the resin obtained is inferior in heat stability.
  • the resin is deteriorated by thermal energy and the resin obtained shows discoloration.
  • the PVC to be used in the method of producing a chlorinated vinvl chloride resin according to Invention I-19 is a resin produced by polymerizing VCM alone or a mixture of VCM and another monomer or other monomers copolymerizable with VCM by a method known in the art.
  • the other monomers copolymerizable with VCM are not particularly restricted but include, for example, alkyl vinyl esters such as vinyl acetate; ⁇ -monoolefins such as ethylene and propylene; vinylidene chloride; styrene; and the like. These may be used singly or two or more of them may be used combinedly.
  • the average degree of polymerization of the above PVC is not particularly restricted but may be 400 to 3,000, which is conventionally employed.
  • the PVC to be used in the practice of Invention I-19 has a BET specific surface area of 1.3 to 8 m 2 /g.
  • the specific surface area is smaller than 1.3 m 2 /g, the proportion of micropores not larger than 0.1 ⁇ m in the interior of PVC particles becomes small, so that uniform chlorination cannot be attained and the heat stability will not be improved. Further, the rate of gelation is slow and this is undesirable from the molding viewpoint.
  • the specific surface area is greater than 8 m 2 /g, the heat stability of prechlorination PVC particles themselves is low and the CPVC obtained is poor in workability.
  • a preferred range is 1.5 to 5 m 2 /g.
  • the carbon element-chlorine element 1S bond energy (eV) peak ratio (chlorine element peak ⁇ 2/carbon element peak) as found by particle surface analysis by ESCA (electron spectroscopy for chemical analysis) should be above 0.6.
  • an additive such as a dispersant, presumably remain adsorbed on the surface of PVC particles and, therefore, not only the rate of chlorination in the succeeding step becomes slow but also the CPVC obtained raises a moldability/fabricability problem and further has inferior heat stability.
  • a peak ratio exceeding 0.7 is preferred.
  • the peak ratio value of 0 means that the surface of PVC particles is covered with some chlorine-free substance other than PVC, while the peak ratio value of 1 means that the surface of PVC resin particles is wholly covered with vinyl chloride components alone.
  • Those PVCs having the above-specified BET specific surface area and 1S bond energy value (eV) peak ratio can be obtained, for example, by aqueous suspension polymerization using a high saponification degree (60 to 90 mole percent) or low saponification degree (20 to 60 mole percent) polyvinyl acetate or both, a higher fatty acid ester or the like as the dispersant and an anionic emulsifier, a nonionic emulsifier or the like as the emulsifier.
  • aqueous suspension polymerization using a high saponification degree (60 to 90 mole percent) or low saponification degree (20 to 60 mole percent) polyvinyl acetate or both, a higher fatty acid ester or the like as the dispersant and an anionic emulsifier, a nonionic emulsifier or the like as the emulsifier.
  • the polymerizer which can be used in producing the above PVC according to Invention I-19 by polymerization is not particularly restricted in shape and structure but may be any of those conventionally used in PVC polymerization, for instance.
  • the agitating blades are not particularly restricted but include those in general use, such as Pfaudler blades, paddle blades, turbine blades, fan turbine blades and bull margin blades, among others. Pfaudler blades are judiciously used, however, and the combined use of baffle plates is not particularly restricted.
  • the PVC is suspended in an aqueous medium and liquid chlorine or gaseous chlorine is introduced into the reactor.
  • the chlorination reaction is carried out at, a temperature within the range of 70 to 135° C.
  • the chlorination reactor to be used in the practice of Invention I-19 may be a glass-lined stainless steel reactor or any of those in common use, for example a titanium reactor.
  • the chlorination is effected by suspending the PVC in an aqueous medium and introducing liquid or gaseous chlorine thereinto, namely by feeding a chlorine source into the chlorination reactor.
  • liquid chlorine is efficient.
  • the chlorine supplement during reaction for adjusting the pressure or with the progress of the chlorination reaction it is also possible to feed an adequate amount of gaseous chlorine by blowing, if necessary together with liquid chlorine.
  • the method of preparing the above suspended PVC is not particularly restricted but a cake-form post polymerization PVC after monomer removal treatment may be used or a PVC once dried may be again suspended in an aqueous medium, or a suspension resulting from removal of substances unfavorable to the chlorination reaction from the polymerization system may be used. It is preferable, however, to use the cake-like postpolymerization PVC after monomer removal treatment.
  • the amount of the aqueous medium to be charged into the reactor is not particularly restricted but, generally, the medium is charged in an amount of 2 to 10 times (by weight) the weight of PVC.
  • thermo chlorination the method comprising exciting resin bonds or chlorine by heating for promoting the chlorination
  • photo-chlorination the method comprising photochemically promoting the chlorination by irradiation with light
  • the method of heating for thermal chlorination is not particularly restricted but mention may be made, for example, of external jacket heating through the reactor wall, interior jacket heating and blowing steam into the reactor.
  • the external jacket system or interior jacket system is effective.
  • thermal energy and light energy such as ultraviolet rays. In that case, however, an apparatus capable of ultraviolet irradiation under high-temperature and high-pressure conditions is required.
  • ultraviolet rays as well as visible light from a mercury lamp, arc lamp, candescent lamp, fluorescent lamp or carbon arc lamp or the like are suited for use and, in particular, ultraviolet rays are effective.
  • the chlorine content of the product CPVC is preferably adjusted to 60 to 72% by weight, more preferably 63 to 70% by weight.
  • the temperature for the above chlorination reaction is 70 to 135° C., preferably 90 to 125° C.
  • a reaction temperature below 70° C. the rate of the chlorination reaction is slow, hence it is necessary to add a large amount of a reaction catalyst, typically a peroxide, for causing the reaction to proceed.
  • a reaction catalyst typically a peroxide
  • the resin obtained is inferior in heat stability.
  • a reaction temperature above 135° C. the resin is deteriorated by thermal energy and a discolored CPVC is obtained.
  • the chlorine to be used in the practice of the invention is not particularly restricted but, as described in Japanese Kokai Publication Hei-06-32822, the chlorine remaining after purging of 5 to 10% by weight of the cylinder chlorine is preferably used.
  • the gauge-pressure in the above reactor is not particularly restricted but, since a higher chlorine pressure causes ready penetration of chlorine into the interior of PVC particles, a pressure within the range of 0.3 to 2 MPa is preferred.
  • the CPVC according to the invention is first characterized by the structure of CPVC particles. Namely, by defining the interior porous state, a ready gelation tendency in the step of molding is secured. In the next place, by defining the exotic structure content in the CPVC molecular chain, high heat stability is secured. In this way, a resin having both high heat stability and ready gelation tendency is provided by the present invention.
  • the particle structure of the PVC has a characteristic feature. Namely, by defining the surface condition and interior porous state, a ready gelation tendency in the step of molding is developed. In the next place, by carrying out the high-temperature chlorination at a specified reaction temperature, high heat stability is developed.
  • This high heat stability development by that high-temperature reaction is due to the fact that the oxidation (formation of exotic structures, typically the carbonyl group) hardly occurs at elevated temperatures (the reaction equilibrium shifts to the direction to suppression of the formation of such structures as the temperature rises).
  • the reaction equilibrium shifts to the direction to suppression of the formation of such structures as the temperature rises.
  • the chlorinated vinyl chloride resin of the invention is a chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin and has a chlorine content of 72 to 76% by weight, a void ratio of 30 to 40% by volume as determined by mercury porosimetry at the pressure 2,000 kg/cm 2 and a volume percentage of voids 0.001 to 0.1 ⁇ m in size of 2 to 15% by volume relative to the total void volume in the pore volume distribution determined by mercury porosimetry in the pressure range of 0 to 2,000 kg/cm 2 .
  • the CPVC of the invention is obtained by chlorinating a resin produced by polymerizing monomeric vinyl chloride (hereinafter referred to as “VCM”) alone or a mixture of VCM and another monomer or other monomers copolymerizable with VCM by a method known in the art.
  • VCM monomeric vinyl chloride
  • the other monomers copolymerizable with VCM are not particularly restricted but include, for example, alkyl vinyl esters such as vinyl acetate; ⁇ -monoolefins such as ethylene and propylene; vinylidene chloride; styrene; and the like. These may be used singly or two or more may be used combinedly.
  • the CPVC of the invention has a chlorine content of 72 to 76% by weight.
  • the chlorine content is less than 72% by weight, it is difficult to fully attain the intended improvement in heat resistance, which should amount to 65 to 80° C. in terms of Vicat softening temperature, for instance, hence it becomes difficult to use the CPVC in those fields where higher heat resistance is required as compared with the group of currently available heat resistant products.
  • the chlorine content is higher than 76% by weight, molding becomes difficult and gelation becomes insufficient. Further, a higher amount of catalyst addition is required for increasing the reactivity and, as a result, the heat stability decreases.
  • the upper limit to the chlorine content is 76% by weight.
  • a preferred chlorine content is within the range of 72 to 74% by weight.
  • the CPVC of the invention has a void ratio of 30 to 40% by volume.
  • the void ratio is determined by mercury porosimetry at the pressure 2,000 kg/cm 2 .
  • the void ratio is less than 30% by volume, the gelation in the step of molding is slow and this is unfavorable to molding.
  • it is above 40% by volume, the biting by the screws in the step of molding becomes worse and the gelation properties are inferior. It is preferably 31 to 38% by volume.
  • the CPVC of the invention has a volume percentage of voids 0.001 to 0.1 ⁇ m in size of 2 to 15% by volume relative to the total void volume in the pore volume distribution determined by mercury porosimetry in the pressure range of 0 to.2,000 kg/cm 2 .
  • the void pore diameter in the interior of resin particles is a function of the pressure of mercury filled into void pores of the resin and, therefore, the pore size distribution can be determined by continuously measuring the mercury filling pressure and mercury weight.
  • the void volume for the range 0.001 to 0.1 ⁇ m is less than 2% by volume relative to the total void volume, the proportion of micropores in the interior of particles is insufficient and the gelation property in the step of molding is inferior.
  • the void volume for the range 0.001 to 0.1 ⁇ m preferably amounts to 3 to 13% by volume of the total void volume.
  • the chlorinated vinyl chloride resin according to Invention II-2 is a chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin and has a chlorine content of 72 to 76% by volume, a void ratio of 30 to 40% by volume as determined by mercury porosimetry at the pressure 2,000 kg cm 2 and a BET specific surface area of 2 to 12 m 2 /g.
  • the CPVC according to Invention II-2 has a BET specific surface area of 2 to 12 m 2 /g.
  • the BET specific surface area is smaller than 2 m 2 /g, the proportion of micropores in the interior of particles is insufficient and, in the step of molding, intraparticle melting becomes difficult to occur, resulting in inferior gelation property.
  • the BET specific surface area is larger than 12 m 2 /g, the heat stability in the step of molding becomes poor due to abrupt frictional heat generation from the inside.
  • a preferred BET specific surface area is 3 to 10 m 2 /g.
  • the chlorinated vinyl chloride resin according to Invention II-3 is a CPVC according to Invention II-1 or Invention II-2 which, in particle surface analysis by ESCA (electron spectroscopy for chemical analysis), shows a carbon element-chlorine element 1S bond energy (eV) peak ratio (chlorine element peak/carbon element peak) of higher than 0.6
  • ESCA electron spectroscopy for chemical analysis
  • eV carbon element-chlorine element 1S bond energy
  • the ratio is more preferably higher than 0.7.
  • CPVCs for which the above peak ratio is above 0.6 there are skinless CPVCs having a small skin area on the surface of CPVC particles.
  • CPVCs having the above-specified void ratio, pore distribution, BET specific surface area and 1S bond energy (eV) peak ratio are obtained by chlorinating a PVC produced by aqueous suspension polymerization using a high saponification degree (60 to 90 mole percent) or low saponification degree (20 to 60 mole percent) polyvinyl acetate or both, a higher fatty acid ester or the like as the dispersant and an anionic emulsifier, a nonionic emulsifier or the like as the emulsifier.
  • the method of producing the CPVC of the invention is not particularly restricted provided that a CPVC having the above-specified properties can be obtained.
  • the method according to Invention II-4 for producing chlorinated vinyl chloride resins is a method of producing a chlorinated vinyl chloride resin by chlorinating a vinyl chloride resin wherein said vinyl chloride resin has a BET specific surface area of 1.3 to 8 m 2 /g and a carbon element-chlorine element 1S bond energy (eV) peak ratio (chlorine element peak ⁇ 2/carbon element peak) of higher than 0.6 as found by particle surface analysis by ESCA (electron spectroscopy for chemical analysis) and the chlorination reaction is carried out by introducing liquid-chlorine or gaseous chlorine into the reactor where the above vinyl chloride resin occurs in a state suspended in an aqueous medium and. effecting the chlorination at a temperature within the range of 70 to 135° C. until a chlorine content of 72 to 76% by weight is attained.
  • eV carbon element-chlorine element 1S bond energy
  • the PVC to be used in carrying out the production method according to Invention II-4 is are in produced by polymerizing, by a method known in the art, VCM alone or a mixture of VCM and another monomer or other monomers copolymerizable with VCM.
  • the other monomers copolymerizable with VCM are not particularly restricted but include, for example, alkyl vinyl esters such as vinyl acetate; ⁇ -monoolefins such as ethylene and propylene; vinylidene chloride; styrene; and the like. These may be used singly or two or more of them may be used combinedly.
  • the average molecular weight of the above PVC is not particularly restricted but may be 400 to 3,000, as is conventional in the art.
  • the PVC to be used in the practice of Invention II-4 has a BET specific surface area of 1.3 to 8 m 2 /g.
  • the specific surface area is smaller than 1.3 m 2 /g, the proportion of micropores not larger than 0.1 ⁇ m in the interior of PVC particles becomes small, so that uniform chlorination cannot be attained and the heat stability will not be improved. Further, the rate of gelation is slow and this is undesirable from the molding viewpoint.
  • the specific surface area is greater than 8 m 2 /g, the heat stability of prechlorination PVC particles themselves is low and the CPVC obtained is poor in workability.
  • a preferred range is 1.5 to 5 m 2 /g.
  • the carbon element-chlorine element 1S bond energy (eV) peak ratio (chlorine element peak ⁇ 2/carbon element peak) as found by particle surface analysis by ESCA (electron spectroscopy for chemical analysis) should be above 0.6.
  • an additive such as a dispersant, presumably remain adsorbed on the surface of PVC particles and, therefore, not only the rate of chlorination in the succeeding step becomes slow but also the CPVC obtained raises a moldability/fabricability problem and further has inferior heat stability.
  • a peak ratio exceeding 0.7 is preferred.
  • the peak ratio value of 0 means that the surface of PVC particles is covered with some chlorine-free substance other than PVC
  • the peak ratio value of 1 means that the surface of PVC resin particles is wholly covered with vinyl chloride components alone.
  • Those PVCs having the above-mentioned BET specific surface area and 1S bond energy value (eV) peak ratio can be obtained, for example, by aqueous suspension polymerization using a high saponification degree (60 to 90 mole percent) or low saponification degree (20 to 60 mole percent) polyvinyl acetate or both, a higher fatty acid ester or the like as the dispersant and an anionic emulsifier, a nonionic emulsifier or the like as the emulsifier.
  • aqueous suspension polymerization using a high saponification degree (60 to 90 mole percent) or low saponification degree (20 to 60 mole percent) polyvinyl acetate or both, a higher fatty acid ester or the like as the dispersant and an anionic emulsifier, a nonionic emulsifier or the like as the emulsifier.
  • the polymerizer which can be used in producing the above PVC according to Invention II-4 by polymerization is not particularly restricted in shape and structure but may be any of those described hereinabove referring to the first aspect of the invention.
  • the PVC is suspended in an aqueous medium and liquid chlorine or gaseous chlorine is introduced into the reactor.
  • the chlorination reaction is carried out at a temperature within the range of 70 to 135° C. until the chlorine content of the resulting CPVC arrives at 72 to 76% by weight.
  • the chlorination reactor to be used in the practice of Invention II-4 is not particularly restricted in material but may be a glass-lined stainless steel reactor or any of those in common use, for example a titanium reactor.
  • the PVC is suspended in an aqueous medium and liquid chlorine or gaseous chlorine is introduced thereinto, namely a chlorine source is fed to the chlorination reactor.
  • liquid chlorine or gaseous chlorine is introduced thereinto, namely a chlorine source is fed to the chlorination reactor.
  • the introduction of liquid chlorine is efficient.
  • the chlorine supplement during reaction for adjusting the pressure or with the progress of the chlorination reaction it is also possible to feed an adequate amount of gaseous chlorine by blowing, if necessary, together with liquid chlorine.
  • the method of preparing the PVC suspended in an aqueous medium is not particularly restricted but a cake-form postpolymerization PVC after monomer removal treatment may be used or a PVC once dried may be again suspended in an aqueous medium, or a suspension resulting from removal of substances undesirable for the chlorination reaction from the polymerization system may be used. It is preferable, however, to use the cake-like postpolymerization PVC after monomer removal treatment.
  • the amount of the aqueous medium to be charged into the reactor is not particularly restricted but, preferably, the medium is charged in an amount of 2 to 10 times (by weight) the weight of PVC.
  • the method of effecting the chlorination in the above suspended state is not particularly restricted but, for example, mention may be made of thermal chlorination and photo-chlorination, among others. Thermal chlorination is preferably employed, however.
  • the chlorine content of the resulting CPVC is adjusted to 72 to 76%, preferably 72 to 74% by weight.
  • the chlorine content is less than 72% by weight, it is difficult to fully attain the intended improvement in heat resistance, which should amount to 65 to 80° C. in terms of Vicat softening temperature, for instance, hence it becomes difficult to use the CPVC in those fields where higher heat resistance is required as compared with the group of currently available heat resistant products.
  • the chlorine content is higher than 76% by weight, molding becomes difficult and gelation becomes insufficient. Further, a higher amount of catalyst addition is required for increasing the reactivity and, as a result, the heat stability decreases.
  • the upper limit to the chlorine content is 76% by weight.
  • a preferred chlorine content is within the range of 72 to 74% by weight.
  • the temperature for the above chlorination reaction is 70 to 135° C., preferably 90 to 125° C.
  • the rate of the chlorination reaction is slow, hence a long period of time is required for the reaction.
  • a reaction temperature above 135SC the resin is deteriorated by thermal energy and a product CPVC is discolored.
  • the CPVC of the invention is characterized by its particle structure. While it is generally difficult to mold a CPVC having a chlorine content of 72% by weight or higher, it is possible according to the present invention to realize ready gelation tendency in the step of molding by causing CPVC particles to have a specific interior porous state and a specific particle surface state. In this way, a resin having both high heat resistance and ready gelation tendency is provided by the present invention.
  • the particle structure of the PVC has a characteristic feature. Namely, by providing a specific surface condition and interior porous state, the ready gelation tendency in the step of molding is increased.
  • the PVC chlorination is carried out at a specific high temperature and to a specified degree of chlorination. While molding generally becomes difficult at a chlorine content of 72% by weight or higher, it is possible according to Invention II-4 to attain ready gelation tendency in the step of molding by combining a structurally characterized PVC and a specific method of chlorination. Thus, it becomes possible according to the invention II-4 to produce a resin having both high heat resistance and ready gelation tendency.
  • the CPVC pipe, CPVC joint and CPVC plate according to the present invention is characterized by having a Vicat softening temperature of not lower than 145° C. as determined under a load of 1 kgf by the method according to JIS K 7206.
  • the CPVC pipe according to Invention III-1 has a Vicat softening temperature of not lower than 145° C. as determined under a load of 1 kgf by the method according to JIS K 7206.
  • the Vicat softening temperature is an indicator of the heat resistance of pipes. Pipes having a Vicat softening temperature lower than 145° C. can hardly be used in the case that a liquid or gas having a temperature of 100° C. or above is passed therethrough and therefore a higher level of heat resistance is required as compared with the fields in which the prior art products are used, typically in the field of hot water supply pipes.
  • the upper limit to the above Vicat softening temperature is desirably as high as possible. Considering the actual molding extrusion technology for pipes, however, the limit is at 185° C.
  • the above CPVC preferably has a chlorine content of 70 to 76% by weight.
  • a chlorine content lower than 70% by weight is insufficient for increasing the heat resistance, namely the above-mentioned Vicat softening temperature at a load of 1 kgf, to a level not lower than 145° C. and, therefore, the resulting products can hardly be used in those fields where still higher heat resistance is required as compared with the currently available heat-resistant product groups.
  • At a content exceeding 76% by weight the molding is difficult and the gelation is insufficient.
  • the above CPVC pipe is sufficient in gelation and has excellently developed shock resistance and other physical properties in spite of the use of a high chlorine content CPVC.
  • the improvement in ready gelation tendency owes to the characteristic interior porous condition and surface condition of CPVC particles.
  • the particle structure of the CPVC particles is characterized by a void ratio of 30 to 40% by volume as determined by mercury porosimetry at the pressure 2,000 kg/cm 2 .
  • a more preferred void ratio is within the range of 31 to 38% by volume.
  • the void volume is less than 30% by volume, the gelation in the step of molding is slow and this is unfavorable for the molding.
  • it is above 40% by volume the biting by the screws in the step of molding becomes poor and the gelation tendency is inferior.
  • the above CPVC has a void volume percentage for the range of 0.001 to 0.1 ⁇ m of 2 to 15% by volume, preferably 3 to 13% by volume, relative to the total void volume in the pore volume distribution determined by the same measurement method as in the void ratio measurement in the pressure range of 0 to 2,000 kg/cm 2 .
  • the void volume for the range of 0.001 to 0.1 ⁇ m the proportion of micropores in the interior of particles is insufficient and the gelation tendency in the step of molding is poor.
  • it is above 15% by volume the diffusion of chlorine in the step of chlorination will not be effected in a balanced manner but the chlorination degree distribution in the interior of particles becomes excessive, hence the heat stability is poor.
  • the above CPVC further has a BET specific surface area within the range of 2 to 12 m 2 /g, more preferably 3 to 10 M 2 /g.
  • a BET specific surface area within the range of 2 to 12 m 2 /g, more preferably 3 to 10 M 2 /g.
  • the above CPVC preferably has a peak ratio (chlorine element peak/carbon element peak) exceeding 0.6, more preferably exceeding 0.65, at the carbon element-chlorine element 1S bond energy value (eV) as determined by particle surface analysis by ESCA (electron spectroscopy for chemical analysis).
  • ESCA electro spectroscopy for chemical analysis
  • CPVCs for which the above peak ratio is above 0.6 there are skinless CPVCs having a small skin area on the surface of CPVC particles.
  • CPVCs having the above-specified void ratio, pore distribution, BET specific surface area and ESCA analysis value are obtained by chlorinating a resin produced by polymerizing VCM alone or a mixture of VCM and another monomer or other monomers copolymerizable with VCM by a method known in the art.
  • the other monomers copolymerizable with VCM are not particularly restricted but include, for example, alkyl vinyl esters such as vinyl acetate; ⁇ -monoolefins such as ethylene and propylene; vinylidene chloride; styrene; and the like. These may be used singly or two or more of them may be used combinedly.
  • the CPVC having the above-specified BET specific surface area and 1S bond energy (eV) peak ratio can be obtained, for example, by aqueous suspension polymerization using a high saponification degree (60 to 90 mole percent) or low saponification degree (20 to 60 mole percent) polyvinyl acetate or both, a higher fatty acid ester or the like as the dispersant and a nonionic emulsifier, an anionic emulsifier or the like as the emulsifier.
  • aqueous suspension polymerization using a high saponification degree (60 to 90 mole percent) or low saponification degree (20 to 60 mole percent) polyvinyl acetate or both, a higher fatty acid ester or the like as the dispersant and a nonionic emulsifier, an anionic emulsifier or the like as the emulsifier.
  • the above chlorination is effected by introducing liquid chlorine or gaseous chlorine into a reactor in which PVC occurs in a state suspended in an aqueous medium.
  • the cake-like resin after monomer removing treatment following PVC polymerization is preferably used.
  • a PVC once dried may be again suspended in an aqueous medium.
  • the suspension obtained after removal of substances unfavorable to the chlorination reaction from the polymerization system may also be used.
  • the reaction is carried out in the manner of thermal chlorination.
  • the method of heating for the thermal chlorination is the same as described referring to the first aspect and second aspect of the invention.
  • the above reaction is carried out at a reaction temperature within the range of 70 to 135° C., more preferably 85 to 120° C.
  • a reaction temperature within the range of 70 to 135° C., more preferably 85 to 120° C.
  • the rate of chlorination reaction is low and, accordingly, a long period of time is required for the reaction.
  • a temperature above 135° C. the decrease in voids in the interior of particles becomes significant through the influence of thermal energy owing to the high temperature reaction, so that sufficient gelation cannot be attained in the step of molding/fabrication. Further, the resin is deteriorated by the thermal energy.
  • the molding can be effected using conventional compounding additives, such as a stabilizer, lubricant, modifier, filler, processing aid, pigment, etc.
  • the molding machine to be used in the above CPVC pipe molding is not particularly restricted but includes, among others, a single-screw extruder, twin-screw two-directional parallel extruder, twin-screw two-directional conical extruder and twin-screw unidirectional extruder.
  • the mold, resin temperature and molding conditions for molding the above CPVC pipe are not particularly restricted.
  • the gist of this invention consists in formulating CPVC having a chlorine content of 70 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC pipe having a Vicat softening temperature of not lower than 145° C.
  • the CPVC pipe according to Invention III-2 has a Vicat softening temperature of not lower than 155° C. as determined under a load of 1 kgf by the method according to JIS K 7206.
  • the pipe can be used in a steam return piping system, for instance.
  • the CPVC to be used in producing the CPVC pipe according to Invention III-2 preferably has a chlorine content of 72 to 76% by weight.
  • a chlorine content lower than 72% by weight is insufficient to attain heat resistance, namely raising the above Vicat softening temperature to l55° C. or above, hence the pipe cannot be used in a steam return piping system.
  • the chlorine content is above 76% by weight, the molding is difficult to conduct and the gelation is insufficient.
  • the particle structure of the CPVC to be used in producing the CPVC pipe according to Invention III-2 is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe of the invention.
  • the CPVC to be used in producing the CPVC pipe according to Invention III-2 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe according to Invention III-1. Since, however, the chlorine content of the CPVC to be used in producing the CPVC pipe according to Invention III-2 is nigher than that of the CPVC to be used in producing the CPVC pipe according to Invention III-1, a more preferred reaction temperature is within the range of 90 to 120° C.
  • the CPVC pipe according to Invention III-2 can be molded in the same manner using the same compounding additives as mentioned above referring to the above-mentioned CPVC pipe of the invention.
  • the gist of Invention III-2 consists in formulating CPVC having a chlorine content of 72 to 76% by weight and having a specific particle inside structure, and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC pipe having a Vicat softening temperature of not lower than 155° C.
  • the CPVC pipe according to Invention III-3 has a Vicat softening temperature of not lower than 170° C. as determined under a load of 1 kgf by the method according to JIS K 7206.
  • the CPVC to be used in producing the CPVC pipe according to Invention III-3 preferably has a chlorine content of 74 to 76% by weight.
  • a chlorine content lower than 74% by weight is insufficient to increase the heat resistance, namely the above-mentioned Vicat softening temperature at a load of 1 kgf, to a level not lower than 170° C. and, therefore, the resulting products can hardly be used in those fields where still higher heat resistance is required as compared with the currently available heat-resistant product groups.
  • At a content exceeding 76% by weight the molding is difficult and the gelation is insufficient.
  • the particle structure of the CPVC to be used in producing the CPVC pipe according to Invention III-3 is also characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe of the invention.
  • the CPVC pipe according to Invention III-3 can be molded in the same manner using the same compounding additives as mentioned above referring to the above-mentioned CPVC pipe of the invention.
  • the gist of Invention III-3 consists in formulating CPVC having a chlorine content of 74 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC pipe having a Vicat softening temperature of not lower than 170° C.
  • the CPVC pipe according to Invention III-4 has a Vicat softening temperature of not lower than 145° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111.
  • the above Charpy impact strength is an indicator of the shock resistance of a pipe and, when the Charpy impact strength is not less than 10 kgf ⁇ cm/cm 2 , the pipe is suited for use for passing a liquid or gas at 100° C. or above therethrough.
  • the CPVC pipe according to Invention III-4 is molded using a CPVC having an increased chlorine content so that the heat resistance may be increased.
  • a highly chlorinated resin results in insufficient gelation in the step of molding and thus gives a brittle pipe with decreased shock resistance. Therefore, an increased amount of a shock resistance improving agent is used in the step of molding but, on the other hand, the use of such agent may decrease the heat resistance.
  • a preferred range is, therefore, 10 to 60 kgf ⁇ cm/cm 2 , more preferably 15 to 50 kgf ⁇ cm/cm 2 .
  • the CPVC to be used in producing the CPVC pipe according to Invention III-4 preferably has a chlorine content of 70 to 76%, like the CPVC according to Invention III-1.
  • the particle structure of the CPVC to be used in producing the CPVC pipe according to Invention III-4, too, is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe of the invention.
  • the CPVC to be used in producing the CPVC pipe according to Invention III-4 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe according to Invention III-1.
  • the CPVC pipe according to Invention III-4 can be molded in the same manner using the same compounding additives as mentioned above referring to the above-mentioned CPVC pipe of the invention.
  • the gist of Invention III-4 consists in formulating CPVC having a chlorine content of 70 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC pipe having a Vicat softening temperature of not lower than 145° C. and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 .
  • Invention III-5 provides the CPVC pipe which has a Vicat softening temperature of not lower than 155° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111.
  • the CPVC preferably has a chlorine content of 72 to 76% by weight, like the CPVC according to Invention III-2.
  • the particle structure of the CPVC to be used in producing the CPVC pipe according to Invention III-5 is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe of the invention.
  • the CPVC to be used in producing the CPVC pipe according to Invention III-5 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe according to Invention III-2.
  • the CPVC pipe according to Invention III-5 can be molded in the same manner using the same compounding additives as mentioned above referring to the above-mentioned CPVC pipe of the invention.
  • the gist of Invention III-5 consists in formulating CPVC having a chlorine content of 72 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC pipe having a Vicat softening temperature of not lower than 155° C. and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 .
  • the CPVC pipe according to Invention III-6 has a Vicat softening temperature of not lower than 170° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not Less than 10 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111.
  • the chlorine content of the CPVC to be used in producing the CPVC pipe according to Invention III-6 is preferably 74 to 76% by weight, like the CPVC according to Invention III-3.
  • the particle structure of the CPVC to be used in producing the CPVC pipe according to Invention III-6, too, is characterized by its particle inside structure and surface. structure, like the CPVC to be used in producing the above-mentioned CPVC pipe of the invention.
  • the CPVC to be used in producing the CPVC pipe according to Invention III-6 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe according to Invention III-3.
  • the CPVC pipe according to Invention III-6 can be molded in the same manner using the same compounding additives as mentioned above referring to the above-mentioned CPVC pipe of the invention.
  • the gist of Invention III-6 consists in formulating CPVC having a chlorine content of 74 to 76% by weight and having a specific particle inside structure and a specific particle surface structure, and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC pipe having a Vicat softening temperature of not lower than 170° C. and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 .
  • the CPVC pipe according to Invention III-7 has a Vicat softening temperature of not lower than 145° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 20 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111.
  • the above Charpy impact strength is an indicator of the shock resistance of a pipe and, when the Charpy impact strength is not less than 20 kgf ⁇ cm/cm 2 , the pipe is particularly suited for use for passing a liquid or gas at 100° C. or above therethrough.
  • the CPVC to be used in producing the CPVC pipe according to Invention III-7 preferably has a chlorine content of 70 to 76% by weight, like the CPVC according to Invention III-1 and Invention III-4.
  • the particle structure of the CPVC to be used in producing the CPVC pipe according to Invention III-7, too, is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe of the invention.
  • the CPVC to be used in producing the CPVC pipe according to Invention III-7 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe according to Invention III-1 and Invention III-4.
  • the CPVC pipe according to Invention III-7 can be molded in the same manner using the same compounding additives as mentioned above referring to the above-mentioned CPVC pipe of the invention.
  • the gist of Invention III-7 consists in formulating CPVC having a chlorine content of 70 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC pipe having a Vicat softening temperature of not lower than 145SC and a Charpy impact strength of not less than 20 kgf ⁇ cm/cm 2 .
  • the CPVC pipe according to Invention III-8 has a Vicat softening temperature of not lower than 155° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 20 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111.
  • the chlorine content of the CPVC to be used in producing the CPVC pipe according to Invention III-8 is preferably 72 to 76% by weight, like the CPVC according to Invention III-2 and Invention III-5.
  • the particle structure of the CPVC to be used in producing the CPVC pipe according to Invention III-8, too, is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe of the invention.
  • the CPVC to be used in producing the CPVC pipe according to Invention III-8 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe according to Invention III-2 and Invention III-5.
  • the CPVC pipe according to Invention III-8 can be molded in the same manner using the same compounding additives as mentioned above referring to the above-mentioned CPVC pipe of the invention.
  • the gist of Invention III-8 consists in formulating CPVC having a chlorine content of 72 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC pipe having a Vicat softening temperature of not lower than 155° C. and a Charpy impact strength of not less than 20 kgf ⁇ cm/cm 2 .
  • the CPVC pipe according to Invention 111-9 has a Vicat softening temperature of not lower than 170° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 20 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111.
  • the CPVC according to Invention III-9 preferably has a chlorine content of 74 to 76% by weight, like the CPVC according to Invention III-3 and Invention III-6.
  • the particle structure of the CPVC to be used in producing the pipe according to Invention III-9, too, is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe of the invention.
  • the CPVC to be used in producing the CPVC pipe according to Invention III-9 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe according to Invention III-3 and Invention III-6.
  • the CPVC pipe according to Invention III-9 can be molded in the same manner using the same compounding additives as mentioned above referring to the above-mentioned CPVC pipe of the invention.
  • the gist of Invention III-9 consists in formulating CPVC having a chlorine content of 74 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC pipe having a Vicat softening temperature of not lower than 170° C. and a Charpy impact strength of not less than 20 kgf ⁇ cm/cm 2 .
  • the CPVC joint according to Invention III-10 has a Vicat softening temperature of not lower than 145° C. as determined under a load of 1 kgf by the method according to JIS K 7206.
  • the Vicat softening temperature is an indicator of the heat resistance of joints. Joints having a Vicat softening temperature lower than 145° C. can hardly be used in those fields of application where a liquid or gas having a temperature of 100° C. or higher is passed therethrough and therefore a higher level of heat resistance is required as compared with the fields in which the prior art products are used, typically in the field of joints for hot water supply systems.
  • the chlorine content of the CPVC to be used according to Invention III-10 is preferably 70 to 76% by weight, like the CPVC according to Invention III-1, Invention III-4 and Invention III-7.
  • the particle structure of the CPVC to be used in producing the CPVC joint according to Invention III-10 is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe of the invention.
  • the CPVC to be used in producing the CPVC joint according to Invention III-10 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe according to Invention III-1, Invention III-4 and Invention III-7.
  • the molding machine to be used in molding the CPVC joint according to Invention III-10 is not particularly restricted but the technique of injection molding is judiciously used as the method of molding.
  • the mold, resin temperature and molding conditions for producing the CPVC joint according to Invention III-10 are not particularly restricted, either.
  • the gist of Invention III-10 consists in formulating CPVC having a chlorine content of 70 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC joint having a Vicat softening temperature of not lower than 145° C.
  • the CPVC joint according to Invention III-11 has a Vicat softening temperature of not lower than 155° C. as determined under a load of 1 kgf by the method according to JIS K 7206.
  • the CPVC according to Invention III-11 preferably has a chlorine content of 72 to 76% by weight, like the CPVC according to Invention III-2, Invention III-5 and Invention III-8.
  • the particle structure of the CPVC to be used in producing the joint according to Invention III-11, too, is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe and CPVC joint of the invention.
  • the CPVC to be used in producing the CPVC joint according to Invention III-11 can be obtained in the same manner as the CPVC to be used in the practice of Invention III-2, Invention III-5 and Invention III-8.
  • the CPVC joint according to Invention III-11 can be molded in the same manner as the above-mentioned CPVC joint of the invention using the same compounding additives as mentioned hereinabove referring to the above-mentioned CPVC pipe and CPVC joint of the invention.
  • the gist of Invention III-11 consists in formulating CPVC having a chlorine content of 72 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC joint having a Vicat softening temperature of not lower than 155° C.
  • the CPVC joint according to Invention III-12 has a Vicat softening temperature of not lower than 170° C. as determined under a load of 1 kgf by the method according to JIS K 7206.
  • the chlorine content of the CPVC to be used in the practice of Invention III-12 is preferably 74 to 76% by weight, like the CPVC to be used in the practice of Invention III-3, Invention III-6 and Invention III-9.
  • the particle structure of the CPVC to be used in producing the CPVC joint according to Invention III-12 is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe and CPVC joint of the invention.
  • the CPVC to be used in producing the CPVC joint according to Invention III-12 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe according to Invention III-3, Invention III-6 and Invention III-9.
  • the CPVC joint according to Invention III-12 can be molded in the same manner as the above-mentioned CPVC joint of the invention using the same compounding additives as mentioned hereinabove referring to the CPVC pipe and CPVC joint of the invention.
  • the gist of Invention III-12 consists in formulating CPVC having a chlorine content of 74 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC joint having a Vicat softening temperature of not lower than 170° C.
  • the CPVC joint according to Invention III-13 has a Vicat softening temperature of not lower than 145° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111.
  • the Charpy impact strength is an indicator of the shock resistance of a joint and, when the Charpy impact strength is not less than 10 kgf ⁇ cm/cm 2 , the joint is suited for use for passing a liquid or gas at 100° C. or above therethrough.
  • the chlorine content of CPVC to be used in the practice of Invention III-13 is preferably 70 to 76% by-weight, like the CPVC to be used in the practice of Invention III-1, Invention III-4, Invention III-7 and Invention III-10.
  • the particle structure of the CPVC to be used in producing the CPVC joint according to Invention III-13, too, is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe and CPVC joint of the invention.
  • the CPVC to be used in producing the CPVC joint according to Invention III-13 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe according to Invention III-1, Invention III-4 and Invention III-7 and the CPVC joint according to Invention III-10.
  • the CPVC joint according to Invention III-13 can be molded in the same manner as the above-mentioned CPVC joint of the invention using the same compounding additives as mentioned hereinabove referring to the CPVC pipe and CPVC joint of the invention.
  • the gist of Invention III-13 consists in formulating CPVC having a chlorine content of 70 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC joint having a Vicat softening temperature of not lower than 145° C. and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 .
  • the CPVC joint according to Invention III-14 has a Vicat softening temperature of not lower than 155° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111.
  • the chlorine content of the CPVC to be used in the practice of Invention III-14 is preferably 72 to 76% by weight, like the CPVC to be used in the practice of Invention III-2, Invention III-5, Invention III-8 and Invention III-11.
  • the particle structure of the CPVC to be used in producing the CPVC joint according to Invention III-14, too, is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe and CPVC joint of the invention.
  • the CPVC to be used in producing the CPVC joint according to Invention III-14 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe according to Invention III-2, Invention III-5 and Invention III-8 and the CPVC joint according to Invention III-11.
  • the CPVC joint according to Invention III-14 can be molded in the same manner as the above-mentioned CPVC joint of the invention using the same compounding additives as mentioned hereinabove referring to the CPVC pipe and CPVC joint of the invention.
  • the gist of Invention III-14 consists in formulating CPVC having a chlorine content of 72 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC joint having a Vicat softening temperature of not lower than 155° C. and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 .
  • the CPVC joint according to Invention III-15 has a Vicat softening temperature of not lower than 170° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 10 kgf cm/cm 2 as determined by the method according to JIS K 7111.
  • the CPVC to be used in the practice of Invention III-15 preferably has a chlorine content of 74 to 76% by weight, like the CPVC to be used in the practice of Invention III-3, Invention III-6, Invention III-9 and Invention III-12.
  • the particle structure of the CPVC to be used in producing the CPVC joint according to Invention III-15 is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe and CPVC joint of the invention.
  • the CPVC to be used in producing the CPVC joint according to Invention III-15 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe according to Invention-III-3, Invention III-6 and Invention III-9 and the CPVC joint according to Invention III-12.
  • the CPVC joint according to Invention III-15 can be molded in the same manner as the above-mentioned CPVC joint of the invention using the same compounding additives as mentioned hereinabove referring to the CPVC pipe and CPVC joint of the invention.
  • the gist of Invention III-15 consists in formulating CPVC having a chlorine content of 74 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC joint having a Vicat softening temperature of not lower than 170° C. and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 .
  • the CPVC joint according to Invention III-16 has a Vicat softening temperature of not lower than 145° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 20 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111.
  • the above Charpy impact strength is an indicator of the shock resistance of a joint and, when the Charpy impact strength is not less than 20 kgf ⁇ cm/cm 2 , the joint is particularly suited for use for passing a liquid or gas at 100° C. or above therethrough.
  • the CPVC to be used in the practice of Invention III-16 preferably has a chlorine content of 70 to 76% by weight, like the CPVC to be used in the practice of Invention III-1, Invention III-4, Invention III-7, Invention III-10 and Invention III-13.
  • the particle structure of the CPVC to be used in producing the CPVC joint according to Invention III-16, too is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe and CPVC joint of the invention.
  • the CPVC to be used in producing the CPVC joint according to Invention III-16 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe according to Invention III-1, Invention III-4 and Invention III-7 and the CPVC joint according to Invention III-10 and Invention III-13.
  • the CPVC joint according to Invention III-16 can be molded in the same manner as the above-mentioned CPVC joint of the invention using the same compounding additives as mentioned hereinabove referring to the CPVC pipe and CPVC joint of the invention.
  • the gist of Invention III-16 consists in formulating CPVC having a chlorine content of 70 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC joint having a Vicat softening temperature of not lower than 145° C. and a Charpy impact strength of not less than 20 kgf ⁇ cm/cm 2 .
  • the CPVC joint according to Invention III-17 has a Vicat softening temperature of not lower than 155° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 20 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111.
  • the CPVC to be used in the practice of Invention III-17 preferably has a chlorine content of 72 to 76%-by weight, like the CPVC to be used in the practice of Invention III-2, Invention III-5, Invention III-8, Invention III-11 and Invention III-14.
  • the particle structure of the CPVC to be used in producing the CPVC joint according to Invention III-17, too, is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe and CPVC joint of the invention.
  • the CPVC to be used in producing the CPVC pipe according to Invention III-17 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe according to Invention III-2, Invention III-5 and Invention III-8 and the CPVC joint according to Invention III-11 and as Invention III-14.
  • the CPVC joint according to Invention I1I-17 can be molded in the same manner as the above-mentioned CPVC joint of the invention using the same compounding additives as mentioned hereinabove referring to the CPVC pipe and CPVC joint of the invention.
  • the gist of Invention III-17 consists in formulating CPVC having a chlorine content of 72 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC joint having a Vicat softening temperature of not lower than 155° C. and a Charpy impact strength of not less than 20 kgf ⁇ cm/cm 2 .
  • the CPVC joint according to Invention III-18 has a Vicat softening temperature of not lower than 170° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 20 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111.
  • the CPVC to be used in the practice of Invention III-18 preferably has a chlorine content of 74 to 76% by weight, like the CPVC to be used in the practice of Invention III-3, Invention III-6, Invention III-9, Invention III-12 and Invention III-15.
  • the particle structure of the CPVC to be used in producing the CPVC pipe according to Invention III-18, too, is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe and CPVC joint of the invention.
  • the CPVC to be used in producing the CPVC joint according to Invention III-18 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe according to Invention III-3, Invention III-6 and Invention III-9 and the CPVC joint according to Invention III-12 and Invention III-15.
  • the CPVC joint according to Invention III-18 can be molded in the same manner as the above-mentioned CPVC joint of the invention using the same compounding additives as mentioned hereinabove referring to the CPVC pipe and CPVC joint of the invention.
  • the gist of Invention III-18 consists in formulating CPVC having a chlorine content of 74 to 76% by weight and having a specific particle inside structure and a specific-particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC joint having a Vicat softening temperature of not lower than 170° C. and a Charpy impact strength of not less than 20 kgf ⁇ cm/cm 2 .
  • the CPVC plate according to Invention III-19 has a Vicat softening temperature of not lower than 145° C. as determined under a load of 1 kgf by the method according to JIS K 7206.
  • the Vicat softening temperature is an indicator of the heat resistance of a resin plate. Plates having a Vicat softening temperature lower than 145° C. can hardly be used in those fields of application where a liquid or gas having a temperature of 100° C. or higher is allowed to flow and therefore a higher level of heat resistance is required as compared with the fields in which the prior art products are used, typically in the field of reservoirs for chemical fluids.
  • the CPVC plate according to Invention III-19 preferably has a chlorine content of 70 to 76% by weight, like the CPVC pipe or CPVC joint according to Invention III-1, Invention III-4, Invention III-7, Invention III-10, Invention III-13 and Invention III-16.
  • the particle structure of the CPVC to be used in producing the CPVC plate according to Invention III-19, too, is, characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe and CPVC joint of the invention.
  • the CPVC to be used in producing the CPVC plate according to Invention III-19 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe or CPVC joint according to Invention III-1, Invention III-4, Invention III-7, Invention III-10, Invention III-13 and Invention III-16.
  • the molding machine to be used in molding the CPVC plate according to Invention III-19 is not particularly restricted but the technique of injection molding is judiciously used as the method of molding.
  • the mold, resin temperature and molding conditions for producing the CPVC plate according to Invention III-19 are not particularly restricted, either.
  • the gist of Invention III-19 consists in formulating CPVC having a chlorine content of 70 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC plate having a Vicat softening temperature of not lower than 145° C.
  • the CPVC plate according to Invention III-20 has a Vicat softening temperature of not lower than 155° C. as determined under a load of 1 kgf by the method according to JIS K 7206.
  • the CPVC plate according to Invention III-20 preferably has a chlorine content of 72 to 76% by weight, like the CPVC pipe or CPVC joint according to Invention III-2, Invention III-5, Invention III-8, Invention III-11, Invention III-14 and Invention III-17.
  • the particle structure of the CPVC to be used in producing the CPVC plate according to Invention III-20 is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe, CPVC joint and CPVC plate of the invention.
  • the CPVC to be used in producing the CPVC plate according to Invention III-20 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe or CPVC joint according to Invention III-2, Invention III-5, Invention III-8, Invention III-11, Invention III-14 and Invention III-17.
  • the CPVC plate according to Invention III-20 can be molded in the same manner as the above-mentioned CPVC plate of the invention using the same compounding additives as mentioned hereinabove referring to the CPVC pipe, CPVC joint and CPVC plate of the invention.
  • the gist of Invention III-20 consists in formulating CPVC having a chlorine content of 72 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC plate having a Vicat softening temperature of not lower than 155° C.
  • the CPVC plate according to Invention III-21 has a Vicat softening temperature of not lower than 170° C. as determined under a load of 1 kgf by the method according to JIS K 7206.
  • the CPVC plate according to Invention III-21 preferably has a chlorine content of 74 to 76% by weight, like the CPVC pipe or CPVC joint according to Invention III-3, Invention III-6, Invention III-9, Invention III-12, Invention III-15 and Invention III-18.
  • the particle structure of the CPVC to be used in producing the CPVC plate according to Invention III-21 is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe, CPVC joint and CPVC plate of the invention.
  • the CPVC to be used in producing the CPVC plate according to Invention III-21 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe or CPVC joint according to Invention III-3, Invention III-6, Invention III-9, Invention III-12, Invention III-15 and Invention III-18.
  • the CPVC plate according to Invention III-21 can be molded in the same manner as the above-mentioned CPVC plate of the invention using the same compounding additives as mentioned hereinabove referring to the CPVC pipe and CPVC plate of the invention.
  • the gist of Invention III-21 consists in formulating CPVC having a chlorine content of 74 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC plate having a Vicat softening temperature of not lower than 170° C.
  • the CPVC plate according to Invention III-22 has a Vicat softening temperature of not lower than 145° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111.
  • the Charpy impact strength is an indicator of the shock resistance of a resin plate and, when the Charpy impact strength is not less than 10 kgf ⁇ cm/cm 2 , the plate is suited for use for holding chemical fluids at 100° C. or above.
  • the chlorine content of the CPVC plate according to Invention III-22 is preferably 70 to 76% by weight, like the CPVC pipe, CPVC joint or CPVC plate according to Invention III-1, Invention III-4, Invention III-7, Invention III-10, Invention III-13, Invention III-16 and Invention III-19.
  • the particle structure of the CPVC to be used in producing the CPVC plate according to Invention III-22 is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe, CPVC joint and CPVC plate of the invention.
  • the CPVC to be used in producing the CPVC plate according to Invention III-22 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe, CPVC joint or CPVC plate according to Invention III-1, Invention III-4, Invention III-7, Invention III-10, Invention III-13, Invention III-16 and Invention III-19.
  • the CPVC plate according to Invention III-22 can be molded in the same manner as the above-mentioned CPVC plate of the invention using the same compounding additives as mentioned hereinabove referring to the CPVC pipe, CPVC joint and CPVC plate of the invention.
  • the gist of Invention III-22 consists in formulating CPVC having a chlorine content of 70 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC plate having a Vicat softening temperature of not lower than 145° C. and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 .
  • the CPVC plate according to Invention III-23 has a Vicat softening temperature of not lower than 155° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 as determined by the method according to JIS K 7111.
  • the chlorine content of CPVC plate according to Invention III-23 is preferably 72 to 76% by weight, like the CPVC pipe, CPVC joint or CPVC plate according to Invention III-2, Invention III-5, Invention III-8, Invention III-11, Invention III-14, Invention III-17 and Invention III-20.
  • the particle structure of the CPVC to be used in producing the CPVC plate according to Invention III-23 is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe, CPVC joint and CPVC plate of the invention.
  • the CPVC to be used in producing the CPVC plate according to Invention III-23 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe, CPVC joint or CPVC plate according to Invention III-2, Invention III-5, Invention III-8, Invention III-11, Invention III-14, Invention III-17 and Invention III-20.
  • the CPVC plate according to Invention III-23 can be molded in the same manner as the above-mentioned CPVC plate of the invention using the same compounding additives as mentioned hereinabove referring to the CPVC pipe, CPVC joint and CPVC plate of the invention.
  • the gist of Invention III-23 consists in formulating CPVC having a chlorine content of 72 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC plate having a Vicat softening temperature of not lower than 155° C. and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 .
  • the CPVC plate according to Invention III-24 has a Vicat softening temperature of not lower than 170° C. as determined under a load of 1 kgf by the method according to JIS K 7206 and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm as determined by the method according to JIS K 7111.
  • the chlorine content of CPVC plate according to Invention III-24 is preferably 74 to 76% by weight, like the CPVC pipe, CPVC joint or CPVC plate according to Invention III-3, Invention III-6, Invention III-9, Invention III-12, Invention III-15, Invention III-18 and Invention III-21.
  • the particle structure of the CPVC to be used in producing the CPVC plate according to Invention III-24, too, is characterized by its particle inside structure and surface structure, like the CPVC to be used in producing the above-mentioned CPVC pipe, CPVC joint and CPVC plate the invention.
  • the CPVC to be used in producing the CPVC plate according to Invention III-24 can be obtained in the same manner as the CPVC to be used in producing the CPVC pipe, CPVC joint or CPVC plate according to Invention III-3, Invention III-6, Invention III-9, Invention III-12, Invention III-15, Invention III-18 and Invention III-21.
  • the CPVC plate according to Invention III-24 can be molded in the same manner as the above-mentioned CPVC plate of the invention using the same compounding additives as mentioned hereinabove referring to the CPVC pipe, CPVC joint and CPVC plate of the invention.
  • the gist of Invention III-24 consists in formulating CPVC having a chlorine content of 74 to 76% by weight and having a specific particle inside structure and a specific particle surface structure and molding the resulting compound. In this way, it becomes possible to provide a highly heat-resistant CPVC plate having a Vicat softening temperature of not lower than 170° C. and a Charpy impact strength of not less than 10 kgf ⁇ cm/cm 2 .
  • thermo resistance temperature as used herein referring to Inventions IV-1 to IV-4 is synonymous as “Vicat softening temperature”. It is determined by measuring Vicat softening temperature by the method of JIS K 7206 (weight 1.0 kgf, rate of temperature rise 50° C./hour) using test specimens prepared by cutting a molding to be tested to 10 mm ⁇ 10 mm.
  • CPVC CPVC obtainable by chlorinating PVC.
  • the PVC prior to chlorination to CPVC which is used in the practice of Inventions IV-1 to IV-4, preferably has a BET specific surface area of 1.3 to 8.0 m 2 /g and a carbon element-chlorine element 1S bond energy (eV) peak ratio (chlorine element peak ⁇ 2/carbon element peak) of above 0.6 as determined in particle surface analysis by ESCA (electron spectroscopy for chemical analysis).
  • the BET specific surface area is less than 1.3 m 2 /g, the proportion of micropores not more than 0.1 ⁇ m in size in the interior of PVC particles is insufficient to attain uniform chlorination and heat stability improvement. Further, the rate of gelation is slow and this is unfavorable from the molding viewpoint.
  • the BET specific surface area is in excess or 8 m 2 /g, the heat stability of PVC particles themselves before chlorination is low and the CPVC obtained becomes poor in workability.
  • a BET specific surface area preferred for the PVC is within the range of 1.5 to 5 m 2 /g.
  • the carbon element-chlorine element 1S bond energy (eV) peak ratio is 0.6 or below, an additive, for example a dispersant, supposedly occur in adsorbed form on the PVC particle surface and, therefore, not only the rate of chlorination in the subsequent step becomes slow but also the CPVC obtained may offer a moldability/fabricability problem and will have poor heat stability. More preferably, the above peak ratio should be above 0.7.
  • the peak ratio value of 0 means that the surface of PVC particles is covered with some chlorine-free substance other than PVC
  • the peak ratio value of 1 means that the surface of PVC particles is wholly covered with vinyl chloride components alone.
  • the above PVC is a resin produced by polymerizing VCM alone or a mixture of VCM and another or other monomers copolymerizable with VCM in the conventional manner (e.g. suspension polymerization, bulk polymerization).
  • the other monomers copolymerizable with VCM are not particularly restricted but include, among others, alkyl vinyl esters such as vinyl acetate; ⁇ -monoolefins such as ethylene and propylene; vinylidene chloride; styrene and the like. These may be used singly or two or more of them may be used in combination.
  • the viscosity average degree of polymerization of the above PVC is not critical but may be within the conventional range of 400 to 2,000.
  • the viscosity average degree of polymerization is determined by the measurement method according to JIS K 6721.
  • the method of chlorinating the above PVC is not particularly restricted but may be any of the methods known in the art.
  • the chlorination can be effected by contacting chlorine with the PVC after setting a state suspended or dissolved in a solvent or in a solid state.
  • the degree of chlorination of the CPVC obtained by the above chlorination reaction is not particularly restricted provided that the molding produced by using that CPVC show a heat resistance temperature of not lower than 125° C.
  • the molding machine to be used in producing the moldings or resin pipes according to Inventions IV-1 to IV-4 is not particularly restricted but, for example, the molding can be effected by using a single-screw extruder, twin-screw two-directional parallel extruder, twin-screw two-directional conical extruder or twin-screw one-directional extruder or the like.
  • the mold, resin temperature and molding conditions in shaping the moldings or resin pipes according to Inventions IV-1 to IV-4 are not particularly restricted provided that the moldings obtained show a surface roughness kmax of not more than 0.5 ⁇ m.
  • the surface roughness of the molding is preferably such that the Rmax is not more than 5 ⁇ m and the Ra is not more than 0.2 ⁇ m.
  • such surface treatment as chromium plating may have been given.
  • the mold lip L/D ratio (L: lip length, D: port thickness) is preferably not less than 15.
  • the temperature at the mold tip is not particularly restricted, either. From the heat stability and long run viewpoint, the molding is preferably carried out within the temperature range of [190 +(t ⁇ 120)/2] C. to [220+(t ⁇ 120)]° C. where t (°C.) is the heat resistance temperature of the moldings.
  • the smoothness of the molding becomes better with the increase in resin temperature unless problems are encountered on the levels of degradation, long-run operability and physical properties. From the heat stability and long run viewpoint, however, it is preferred that the molding be carried out within the temperature range of [195 +(t ⁇ 120)/2]° C. to [210 +(t ⁇ 120)]° C. where t (°C.) is the heat resistance temperature of the molding.
  • the heat-resistant vinyl chloride resin molding according to Invention IV-2 and the heat-resistant vinyl chloride resin pipe according to Invention IV-4 are further characterized by a decomposition time of not shorter than 30 minutes as determined in an oven at 200° C.
  • the “decomposition time of not shorter than 30 minutes” means that when a test specimen is allowed to stand in an oven at 200° C., such a phenomenon as foaming, darkening or discoloration will not occur in a time period shorter than 30 minutes.
  • the reason why the decomposition time is restricted to not shorter than 30 minutes is that when the molding temperature is raised significantly, moldings having a heat resistance temperature not lower than 125° C.
  • an inside surface roughness Rmax of not more than 0.5 ⁇ m may be obtained but for a while but it becomes somewhat difficult to mold such products continuously over several hours and that, for enabling several hours of long run molding, the residual heat stability of molded products in an oven at 200° C. should be not shorter than 30 minutes as expressed in terms of decomposition time.
  • the heat-resistant vinyl chloride resin molding according to Invention IV-1 has a heat resistance temperature of not lower than 125° C. and a surface roughness Rmax of not more than 0.5 ⁇ m and therefore can be used at higher temperatures and, further, at higher pressure and stress, as compared with the prior art products having surface smoothness, hence the reliability can be markedly improved under the same use conditions.
  • the resin itself can contribute to manifestation of good smoothness and, for attaining a surface roughness Rmax of not more than 0.5 ⁇ m, it is now not necessary to significantly raise the resin temperature and mold temperature. As a result, smoothness can be provided while the long run operability and heat stability are maintained.
  • the heat-resistant vinyl chloride resin molding according to Invention IV-2 produces all the effects of the above-mentioned heat-resistant vinyl chloride resin molding according to Invention IV-1 and further, with the heat-resistant vinyl chloride resin molding according to Invention IV-2, the resin itself can contribute to manifestation of good smoothness and, attaining a surface roughness Rmax of not more than 0.5 ⁇ m does not involve significantly increase in the resin temperature and mold temperature. Therefore, the molding has good residual heat stability (decomposition time) and it is possible to provide smoothness while the long run operability is maintained longer.
  • the heat-resistant vinyl chloride resin pipe according to Invention IV-3 has a heat resistance temperature of not lower than 125° C., so that it can be used at still higher temperatures and at a higher pressure and stress as compared with the conventional vinyl chloride resin pipes and, under the same use conditions, the reliability can be markedly improved. Since its inside surface roughness Rmax is not more than 0.5 ⁇ m, the proliferation of bacteria and other microorganisms in the pipe can be inhibited.
  • the resin itself can contribute to good smoothness manifestation and, attaining a surface roughness Rmax of not more than 0.5 ⁇ m does not involve significantly increase in the resin temperature and mold temperature. As a result, smoothness can be provided while the long run operability and heat stability are maintained.
  • the heat-resistant vinyl chloride resin pipe according to Invention IV-4 produces all the effects of the above-mentioned heat-resistant vinyl chloride resin molding according to Invention IV-2 and, further, the inside surface roughness Rmax thereof is not more than 0.5 ⁇ m, bacteria and other microorganisms can be inhibited from propagating in the pipe. Furthermore, the elution of metals is slight and the pipe has smoothness as well, so that it is best suited for use as a piping material for ultrapure water.
  • the heat-resistant vinyl chloride resin pipe according to Invention IV-5 is produced by molding a heat-resistant vinyl chloride resin obtained by chlorinating a vinyl chloride resin having a viscosity average degree of polymerization of 900 to 1, 100 to a chlorine content of 66.0 to 67.5% by weight.
  • the heat-resistant vinyl chloride resin to be used in producing the heat-resistant vinyl chloride resin pipe according to Invention IV-5 is limited to CPVC obtained by chlorinating PVC.
  • the surface condition, particle structure or the like of the PVC before chlorination to the CPVC to be used in the practice of Invention IV-5 is not particularly restricted.
  • the above-mentioned PVC is a resin produced by polymerizing VCM alone or a mixture of VCM and one or more other monomers copolymerizable with VCM in the conventional manner (e.g. by suspension polymerization, bulk polymerization).
  • the other monomers copolymerizable with VCM are not particularly restricted but include, among others, alkyl vinyl esters such as vinyl acetate; ⁇ -monoolefins such as ethylene and propylene; vinylidene chloride; styrene and the like. These may be used singly or two or more of them may be used combinedly.
  • the viscosity average degree of polymerization of the above PVC is restricted to 900 to 1, 100.
  • the SC resistance will become low and it will be impossible to produce resin pipes having sufficient fatigue strength.
  • it is above 1, 100, the problem of decreased smoothness or unevenness may arise.
  • the viscosity average degree of polymerization is measured by the method according to JIS K 6721.
  • the method of chlorinating the above PVC is not particularly restricted but any of the methods known in the art can be used.
  • the chlorination can be effected by contacting chlorine with the PVC after setting a state suspended or dissolved in a solvent or in a solid state.
  • the chlorine content (degree of chlorination) of the CPVC obtained by the chlorination reaction is restricted to 66.0 to 67.5% by weight.
  • the chlorine content is determined by the method according to JIS K 7229.
  • compounding additives generally used in vinyl chloride resins such as stabilizers, lubricants, pigments, modifiers, antistatic agents, fillers and the like, may be incorporated when necessary in amounts which will not defeat the objects of the invention.
  • the molding machine to be used in producing the resin pipe according to Inventions IV-5 is not particularly restricted but, for example, the molding can be effected by using a single-screw extruder, twin-screw two-directional parallel extruder, twin-screw two-directional conical extruder or twin-screw one-directional extruder or the like.
  • the mold, resin temperature and molding conditions in molding the resin pipe according to Inventions IV-5 are not particularly restricted.
  • the surface roughness of the mold is preferably such that the Rmax is not more than 5 ⁇ m and the Ra is not more than 0.2 ⁇ m.
  • such surface treatment as chromium plating may have been given.
  • the mold lip L/D ratio (L: lip length, D: port thickness) is preferably not less than 15.
  • the temperature at the mold tip is not particularly restricted, either. From the heat stability and long run viewpoint, the molding is preferably carried out within the temperature range of [190 +(t ⁇ 120)/2]° C. to [220 +(t ⁇ 120)]° C. where t (°C.) is the heat resistance temperature of the resin pipe.
  • the smoothness of the resin pipe becomes better with the increase in resin temperature unless problems are encountered on the levels of degradation, long-run operability and physical properties. From the heat stability and long run viewpoint, however, it is preferred that the molding be carried out within the temperature range of [195 +(t ⁇ 120)/2]° C. to [210 +(t ⁇ 120)]° C. where t (°C.) is the heat resistance temperature of the resin pipe.
  • the heat-resistant vinyl chloride resin pipe according to Invention IV-5 has a surface roughness Pmax of not more than 0.5 ⁇ m, without involving significant increases in resin temperature and mold temperature, since the resin itself can contribute to good smoothness manifestation. Therefore, the heat-resistant vinyl chloride resin pipe according to Invention IV-5 has good residual heat-stability and has been provided with smoothness, with the long run operability and heat stability being maintained. Accordingly, the heat-resistant vinyl chloride resin pipe according to Invention IV-5 is judiciously used, among others, as a piping Material for ultrapure water supply for plant use, where good smoothness, heat resistance and SC resistance are simultaneously required.
  • the heat-resistant vinyl chloride resin pipe according to Invention IV-6 is a heat-resistant vinyl chloride resin pipe according to Invention IV-3, Invention IV-4 or Invention IV-5 which is to serve as a piping material for pure water distribution.
  • the heat-resistant vinyl chloride resin pipe according to Invention IV-6 has a surface roughness Rmax of not more than 0.5 ⁇ m, without involving significant increases in resin temperature and mold temperature since the resin itself can contribute to good smoothness manifestation. Therefore, the heat-resistant vinyl chloride resin pipe according to Invention IV-6 has been provided with smoothness, with the long run operability and heat stability be maintained. Accordingly, the heat-resistant vinyl chloride resin pipe according to Invention IV-6 is judiciously used as a piping material for pure water supply, among others.
  • a polymerizer pressure-resistant autoclave; capacity 100 liters was charged with 50 kg of deionized water as well as 700 ppm (on vinyl chloride monomer basis) of partially saponified polyvinyl acetate with an average saponification degree of 76 mole percent and a polymerization degree of 700, 150 ppm (on vinyl chloride monomer basis) of polyoxyethylene alkyl ether sulfate salt and 500 ppm (on vinyl chloride monomer basis) of tert-butyl peroxyneodecanoate. Then, the polymerizer was deaerated to 45 mmHg and, thereafter, 33 kg of vinyl chloride monomer was charged thereinto and stirring was initiated.
  • the polymerizer was heated to 57° C. to thereby initiate the polymerization and this temperature was maintained until termination of the polymerization reaction.
  • the ESCA value indicative of the extent of skin layer occurrence in the PVC resin obtained was 0.65.
  • the BET specific surface area was 1.4 m 2 /g.
  • the ESCA value and BET specific surface area were determined by the methods mentioned later herein.
  • a glass-lined reactor (capacity 300 liters) was charged with 150 kg of deionized water and 45 kg of the PVC resin obtained in the above manner, the PVC resin was dispersed in water by stirring and then the reactor was heated and the inside temperature was maintained at 70° C. Then, nitrogen gas was blown into the reactor for purging the reactor inside with nitrogen gas. Then, chlorine gas was blown into the reactor and the chlorination of the PVC resin was effected while irradiating the reactor inside with ultraviolet rays using a mercury lamp.
  • the chlorination reaction was continued while checking the progress of the chlorination reaction by determining the hydrochloric acid concentration in the reactor and, when the chlorine content of the product CPVC resin arrived at 66.5% by weight, the supply of chlorination gas was discontinued and thus the chlorination reaction was finished.
  • the unreaction chlorine was eliminated by blowing nitrogen gas into the reactor, the resin obtained was neutralized with sodium hydroxide, then washed with water, dehydrated and dried to give a CPVC resin as a powder.
  • the chlorine content of the CPVC resin was. 66.5% by weight.
  • a PVC resin was prepared in the same manner as in Example 1 except that the partially saponified polyvinyl acetate was used in an amount of 800 ppm.
  • a CPVC resin was prepared in the same manner as in Example 1
  • a PVC resin was prepared in the same manner as in Example 1 except that the partially saponified polyvinyl acetate was used in an amount of 400 ppm.
  • a CPVC resin was prepared in the same manner as in Example 1.
  • a polymerizer pressure-resistant autoclave; capacity 100 liters was charged with 50 kg of deionized water as well as 750 ppm (on vinyl chloride monomer basis) of partially saponified polyvinyl acetate with an average saponification degree of 72 mole percent and a polymerization degree of 750, 150 ppm. (on vinyl chloride monomer basis) of polyoxyethylene alkyl ether sulfate salt and 500 ppm (on vinyl chloride monomer basis) of tert-butyl peroxyneodecanoate. Then, the polymerizer was deaerated to 45 mmHg and, thereafter, 33 kg of vinyl chloride monomer was charged thereinto and stirring was initiated.
  • the polymerizer was heated to 57° C. to thereby initiate the polymerization and this temperature was maintained until termination of the polymerization reaction.
  • a glass-lined reactor (capacity 300 liters) was charged with 150 kg of deionized water and 45 kg of the PVC resin obtained in the above manner, the PVC resin was dispersed in water by stirring and then the reactor was heated and the inside temperature was maintained at 70° C. Then, nitrogen gas was blown into the reactor for purging the reactor inside with nitrogen gas. Then, chlorine gas was blown into the reactor and the chlorination of the PVC resin was carried out. In this chlorination, the reaction was allowed to proceed while irradiating the reactor inside with ultraviolet rays using a mercury lamp.
  • the chlorination reaction was continued while checking the progress of the chlorination reaction by determining the hydrochloric acid concentration in the reactor and, when the chlorine content of the product CPVC resin arrived at 66.5% by weight, the supply of chlorination gas was discontinued and thus the chlorination reaction was finished.
  • the unreaction chlorine was eliminated by blowing nitrogen gas into the reactor, the resin obtained was neutralized with sodium hydroxide, then washed with water, dehydrated and dried to give a CPVC resin as a powder.
  • the chlorine content of the CPVC resin was 67.5% by weight.
  • PVC resins were prepared by carrying out the polymerization appropriately using partially saponified polyvinyl acetate and polyoxyethylene alkyl ether sulfate salt.
  • CPVCs were prepared in the same manner as in Example 1.
  • a polymerizer pressure-resistant autoclave; capacity 100 liters was charged with 50 kg of deionized water, 750 ppm (on vinyl chloride monomer basis) of partially saponified polyvinyl acetate with an average saponification degree of 72 mole percent and a polymerization degree of 750, 150 ppm (on vinyl chloride monomer basis) of polyoxyethylene alkyl ether sulfate salt and 500 ppm. (on vinyl chloride monomer basis) of tert-butyl peroxyneodecanoate. Then, the polymerizer was deaerated to 45 mmHg and, thereafter, 33 kg of vinyl chloride monomer was charged thereinto and stirring was initiated.
  • the polymerizer was heated to 57° C. to thereby initiate the polymerization and this temperature was maintained until termination of the polymerization reaction.
  • the ESCA value indicative of the extent of skin layer occurrence in the PVC resin obtained was 0.80.
  • the BET specific surface area was 2.5 m 2 /g.
  • the ESCA value and BET specific surface area were determined by the methods mentioned later herein.
  • a glass-lined reactor (capacity 300 liters) was charged with 150 kg of deionized water and 45 kg of the PVC resin obtained in the above manner, the PVC resin was dispersed in water by stirring and then the reactor was heated and the inside temperature was maintained at 110° C. Then, nitrogen gas was blown into the reactor for purging the reactor inside with nitrogen gas. Then, chlorine gas was blown into the reactor and the chlorination of the PVC resin was carried out. The chlorination reaction was continued while checking the progress of the chlorination reaction by determining the hydrochloric acid concentration in the reactor and, when the chlorine content of the product CPVC resin arrived at 66.5% by weight, the supply of chlorination gas was discontinued and thus the chlorination reaction was finished.
  • the unreaction chlorine was eliminated by blowing nitrogen gas into the reactor, the resin obtained was neutralized with sodium hydroxide, then washed with water, dehydrated and dried to give a CPVC resin as a powder.
  • the chlorine content of the CPVC resin was 65.5% by weight.
  • the PVC resin preparation in Examples 6 to 8 was made in the same manner as in Example 5.
  • Example 6 The CPVC resin preparation in Example 6 was made in the same manner as in Example 5 except that the reactor inside temperature was maintained at 70° C. for 1 hour and, after starting the chlorination reaction, it was raised to 110° C. in minutes and the chlorination was continued at that temperature.
  • the chlorine content was 67.5% by weight.
  • Example 7 The CPVC resin preparation in Example. 7 was made in the same manner as in Example 5 except that the reactor inside temperature was maintained at 70° C. for 30 minutes and, after starting the chlorination reaction, it was rapidly raised to 90° C. and the chlorination was continued at that temperature for 30 minutes and then the temperature was further raised to 110° C. rapidly and the chlorination was continued at that temperature.
  • the chlorine content was 68.5% by weight.
  • the CPVC resin preparation in Example 8 was made in the same manner as in Example 5 except that the reactor inside temperature was maintained at 70° C. and, in initiating the chlorination reaction, the reactor inside was irradiated with ultraviolet rays using a mercury lamp to allow the reaction to proceed and, after 1 hour, the temperature was rapidly raised to 110° C. and the chlorination was continued at that temperature.
  • the chlorine content was 66.5% by weight.
  • the polymerizer was heated to 57° C. to thereby initiate the polymerization and this temperature was maintained until termination of the polymerization reaction.
  • the ESCA value indicative of the extent of skin layer occurrence in the PVC resin obtained was 0.2.
  • the BET specific surface area was 0.7 m 2 /g.
  • the ESCA value and BET specific surface area were determined by the methods mentioned later herein.
  • the CPVC resin preparation was made in the same manner as in Example 5 and, at the time when the chlorine content was 66.5% by weight, the chlorination reaction was terminated and the resin was recovered by the same treatment as mentioned above.
  • the PVC resin preparation was made in the same manner as in Comparative Example 5.
  • the surface of PVC resin particles was scanned by ESCA (electron spectroscopy for chemical analysis) and the vinyl chloride resin component on the particle surface was quantitatively analyzed based on the amount of chlorine as estimated from the peak areas for C 15 (carbon), Cl 15 (chlorine) and O 15 (oxygen)
  • test sample About 2 g of the test sample was placed in a sample tube and the sample was deaerated under vacuum at 70° C. for 3 hours (pretreatment), and the sample was accurately weighed. After completion of the pretreatment, the sample was mounted on the measuring part (40° C. thermostat) and the measurement was started. After measurement, BET plotting was carried out using the data on the adsorption side of the adsorption isotherm, and the specific surface area was calculated.
  • the above resin composition was fed to a kneader comprising two 8-inch rolls and kneaded at a roll surface temperature of 205° C. and, after the work was wrapped around the roll, small segments of the CPVC resin sheet were cut out at 3-minute intervals while giving cuts to the CPVC resin sheet on the roll at 30-second intervals.
  • the resin sheet segments cut out were examined for discoloration and the heat stability was evaluated in terms of the time until the resin had assumed a dark brown color.
  • Test samples 15 mm square in size, were cut out from the 5-mm-thick CPVC sheet produced in the above heat stability test and tested according to JIS K 7206 (weight 1.0 kgf).
  • the PVC resin sample was sealed in a gelatin capsule together with an acrylic monomer and allowed to stand at ordinary temperature for 24 hours for allowing the acrylic monomer to polymerize. Thereafter, the capsule was cut to a thickness of about 90 nm using an ultramicrotome (product of LKB Instruments) and the thus-prepared ultrathin section was mounted on a grid mesh and observed under a transmission electron microscope (model JEM-1010, product of Nippon Denshi) The magnification was ⁇ 5,000.
  • the void ratio was determined using a mercury porosimeter and measuring the volume of mercury filled in 100 g of the PVC resin at 2,000 kg/cm 2 .
  • the void ratio is the percent volume of voids relative to the volume of resin particles.
  • the mean pore size and pore distribution were determined by continuously measuring the mercury volume during the process of raising the pressure from 0 to 2,000 kg/cm 2 on the occasion of void ratio measurement to thereby determine the pore size distribution, and the mean pore size was then calculated.
  • the CPVC was dissolved in tetrahydrofuran and a solution with a concentration of 1 g/kg was prepared.
  • the absorbance at 235 nm was measured (cell length 1 cm, measuring temperature 23° C.).
  • the apparatus used was Hitachi model “U-3300”.
  • a polymerizer pressure-resistant autoclave; capacity 100 liters was charged with 50 kg of deionized water, 450 ppm (on vinyl chloride monomer basis) of partially saponified polyvinyl acetate (average saponification degree 72 mole percent; polymerization degree 700), 1,800 ppm (on same basis) of sorbitan monolaurate, 1,200 ppm (on same basis) of lauric acid, 200 ppm (on same basis) of polyacrylamide (Brookfield viscosity of 0. 1% (by weight) aqueous solution: 51 cps at 20° C. and 1 atmosp here) and 550 ppm (on same basis) of tert-butyl peroxyneodecanoate. Then, the polymerizer was deaerated to 45 mmHg and, thereafter, 33 kg of vinyl chloride monomer was charged thereinto and stirring was started.
  • the polymerizer was heated to 57° C. to thereby initiate the polymerization and this temperature was maintained until termination of the polymerization reaction.
  • the reaction was discontinued, the unreacted monomer in the polymerizer was recovered, and the polymer slurry was then discharged out of the system and dehydrated and dried to give a PVC resin.
  • the PVC resin obtained had a BET specific surface area of 4.1 m 2 /g.
  • the ESCA value indicative of the extent of skin layer occurrence was 0.85.
  • T he agglomerate diameter was as shown in Table 1. The BET specific surface area, ESCA value and agglomerate diameter were determined by the methods mentioned herein.
  • a glass-lined reactor (capacity 300 liters) was charged with 150 kg of deionized water and 45 kg of the PVC resin obtained in the above manner, the PVC resin was dispersed in water by stirring and then the reactor was heated and the temperature was maintained at 110° C. Then, nitrogen gas was blown into the reactor for purging the reactor inside with nitrogen gas. Then, chlorine gas was blown into the reactor and the chlorination of the PVC resin was carried out. The chlorination reaction was continued while checking the progress of the chlorination reaction by determining the hydrochloric acid concentration in the reactor and, when the chlorine content of the product CPVC resin arrived at 68.0% by weight, the supply of chlorination gas was discontinued and thus the chlorination reaction was finished.
  • the unreaction chlorine was eliminated by blowing nitrogen gas into the reactor, the resin obtained was neutralized with sodium hydroxide, then washed with water, dehydrated and dried to give a CPVC resin as a powder.
  • the chlorine content of the CPVC resin was 68.0% by weight.
  • the PVC resin preparation was made in the same manner as in Example 9.
  • the CPVC resin preparation was made in the following manner.
  • a glass-lined reactor (capacity 300 liters) was charged with 150 kg of deionized water and 45 kg of the PVC resin obtained in the above manner, the PVC resin was dispersed in water by stirring and then the reactor was heated and the temperature was maintained at 70° C. Then, nitrogen gas was blown into the reactor for purging the reactor in sidewith nitrogen gas. Then, chlorine gas was blown into the reactor and the chlorination of the PVC resin was effected by irradiating the reactor inside with ultraviolet rays using a mercury lamp.
  • the chlorination reaction was continued while checking the progress of the chlorination reaction by determining the hydrochloric acid concentration in the reactor and, when the chlorine content of the product CPVC resin arrived at 68.0% by weight, the supply of chlorination gas was discontinued and thus the chlorination reaction was finished.
  • a CPVC resin as a powder.
  • the chlorine content of the CPVC resin was 68.0% by weight.
  • the PVC resin preparation was made in the same manner as in Example 9 except that the partially saponified polyvinyl acetate (average degree of saponification 72 mole percent, degree of polymerization 700) was used in an amount of 450 ppm and sorbitan monolaurate in an amount of 1,800 ppm.
  • the CPVC resin preparation was made in the same manner as in Example 10.
  • the PVC resin preparation was made in the same manner as in Example 9 except that the partially saponified polyvinyl acetate (average degree of saponification 72 mole percent, degree of polymerization 700) was used in an amount of 1,100 ppm and sorbitan monolaurate in an amount of 1,200 ppm.
  • the CPVC resin preparation was made in the same manner as in Example 9.
  • the PVC resin preparation was made in the same manner as in Example 9 except that 250 ppm of another partially saponified polyvinyl acetate species (average degree of saponification 76 mole percent, degree of polymerization 1,000) was used and 40 ppm of polyoxyethylene alkyl ether sulfate salt was used in lieu of sorbitan monolaurate.
  • the CPVC resin preparation was made in the same manner as in Example 9.
  • the PVC resin preparation was made in the manner mentioned below.
  • the CPVC resin preparation was made in the same manner as in Example 10.
  • a polymerizer pressure-resistant autoclave; capacity 100 liters
  • the polymerizer was deaerated to 45 mmHg and, thereafter, 33 kg of vinyl chloride monomer was charged thereinto and stirring was started.
  • the polymerizer was heated to 57° C. to thereby initiate the polymerization and this temperature was maintained until termination of the polymerization reaction.
  • the reaction was discontinued, the unreacted monomer in the polymerizer was recovered, and the polymer slurry was then discharged out of the system and dehydrated and dried to give a PVC resin.
  • the PVC resin obtained had a BET specific surface area of 0.50 m 2 /g.
  • the ESCA value indicative of the extent of skin layer occurrence was 0.11.
  • the agglomerate diameter was as shown in Table 1. The BET specific surface area, ESCA value and agglomerate diameter were determined by the methods mentioned above.
  • the PVC resin preparation was made in the manner mentioned below.
  • the CPVC resin preparation was made in the same manner as in Example 9.
  • a polymerizer pressure-resistant autoclave; capacity 100 liters
  • the polymerizer was deaerated to 45 mmHg and, thereafter, 33 kg of vinyl chloride monomer was charged thereinto and stirring was started.
  • the polymerizer was heated to 57° C. to thereby initiate the polymerization and this temperature was maintained until termination of the polymerization reaction.
  • the reaction was discontinued, the unreacted monomer in the polymerizer was recovered, and the polymer slurry was then discharged out of the system and dehydrated and dried to give a PVC resin.
  • the PVC resin obtained had a BET specific surface area of 0.7 m 2 /g.
  • the ESCA value indicative of the extent of skin layer occurrence was 0.2.
  • the agglomerate diameter was as shown in Table 1. The BET specific surface area, ESCA value and agglomerate diameter were determined by the methods mentioned above.
  • a polymerizer pressure-resistant autoclave; capacity 100 liters was charged with 50 kg of deionized water, 450 ppm (on vinyl chloride monomer basis) of partially saponified polyvinyl acetate (average saponification degree 72 mole percent; polymerization degree 700), 1,200 ppm (on same basis) of sorbitan monolaurate, 1,200 ppm (on same basis) of lauric acid, 150 ppm (on same basis) of polyacrylamide (Brookfield viscosity of 0.1% (by weight) aqueous solution: 51 cps at 20° C. and 1 atmosphere) and 550 ppm (on same basis) of tert-butyl peroxyneodecanoate. Then, the polymerizer was deaerated to 45 mmHg and, thereafter, 33 kg of vinyl chloride monomer was charged thereinto and stirring was started.
  • the polymerizer was heated to 57° C. to thereby initiate the polymerization and this temperature was maintained until termination of the polymerization reaction.
  • the reaction was discontinued, the unreacted monomer in the polymerizer was recovered, and the polymer slurry was then discharged out of the system and dehydrated and dried to give a PVC resin.
  • the PVC resin obtained had a BET specific surface area of 3.7 m 2 /g.
  • the ESCA value indicative of the extent of skin layer occurrence was 0.80.
  • the void ratio was 35.1% by volume.
  • a glass-lined reactor (capacity 300 liters) was charged with 150 kg of deionized water and 45 kg of the PVC resin obtained in the above manner, the PVC resin was dispersed in water by stirring and then the reactor was heated and the temperature was maintained at 90° C. Then, nitrogen gas was blown into the reactor for purging the reactor inside with nitrogen gas. Then, chlorine gas was blown into the reactor and the chlorination of the PVC resin was carried out.
  • an aqueous solution of hydrogen peroxide was added at a rate of 25 ppm/Hr relative to the charged resin amount after arrival of the chlorine content at 61.0% by weight.
  • the chlorination reaction was continued while checking the hydrochloric acid concentration in the reactor and, when the chlorine content of the product CPVC resin reached 68.5% by weight, the chlorine gas feeding was discontinued and the chlorination reaction was terminated.
  • the chlorine content of the CPVC resin obtained was 68.5% by weight.
  • the void ratio for the pore size range of 0.001 to 0.1 ⁇ m was 15% by volume relative to the total void volume.
  • the PVC resin preparation was made in the same manner as in Example 13.
  • the CPVC resin preparation was made in the manner mentioned below.
  • a glass-lined reactor (capacity 300 liters) was charged with 150 kg of deionized water and 45 kg of the PVC resin obtained in the above manner, the PVC resin was dispersed in water by stirring and then the reactor was heated and the reactor inside was maintained at 70° C. Then, nitrogen gas was blown into the reactor for purging the reactor inside with nitrogen gas. Then, chlorine gas was blown into the reactor and the chlorination of the PVC resin was effected while the reactor inside was irradiated with ultraviolet rays using a mercury lamp.
  • the chlorination reaction was continued while checking the progress of the chlorination reaction by determining the hydrochloric acid concentration in the reactor and, when the chlorine content of the product CPVC resin reached 68.5% by weight, the chlorine gas feeding was discontinued and the chlorination reaction was terminated.
  • the chlorine content of the CPVC resin obtained was 68. 5% by weight.
  • the void ratio for the pore size range of 0.001 to 0.1 ⁇ m was 17.2% by volume relative to the total void volume.
  • the PVC resin preparation was made in the same manner as in Example 13 except that the concentration of partially saponified polyvinyl acetate (average saponification degree 72 mole percent; polymerization degree 700) was 400 ppm and the concentration of sorbitan monolaurate was 1,500 ppm.
  • the CPVC resin preparation was made in the same manner as in Example 13.
  • the PVC resin preparation was made in the same manner as in Example 13 except that the concentration of partially saponified polyvinyl acetate (average saponification degree 72 mole percent; polymerization degree 700) was 1,000 ppm and the concentration of sorbitan monolaurate was 900 ppm.
  • the CPVC resin preparation was made in the same manner as in Example 14.
  • the PVC resin preparation was made in the same manner as in Example 13 except that a different partially saponified polyvinyl acetate species having an average saponification degree of 76 mole percent and a polymerization degree of 1,000 was used in an amount of 700 ppm and 140 ppm of polyoxyethylene alkyl ether sulfate salt was used in lieu of sorbitan monolaurate.
  • the CPVC resin preparation was made in the same manner as in Example 13.
  • the PVC resin preparation was made in the same manner as in Example 13 except that the partially saponified polyvinyl acetate (average saponification degree 72 mole percent; polymerization degree 700) was used in an amount of 450 ppm and sorbitan monolaurate was used in an amount of 1,200 ppm.
  • the CPVC resin preparation was made in the same manner as in Example 14.
  • the PVC resin preparation was made in the manner mentioned below.
  • the CPVC resin preparation was made in the same manner as in Example 14.
  • a polymerizer pressure-resistant autoclave; capacity 100 liters
  • 50 kg of deionized water and 1,200 ppm (on vinyl chloride monomer basis) of partially saponified polyvinyl acetate (average saponification degree 72 mole percent; polymerization degree 750) as suspending and dispersing agent, and 550 ppm (on vinyl chloride monomer basis) of tert-butyl peroxyneodecanoate was added.
  • the polymerizer was deaerated to 45 mmHg and, thereafter, 33 kg of vinyl chloride monomer was charged thereinto and stirring was started.
  • the polymerizer was heated to 57° C. to thereby initiate the polymerization and this temperature was maintained until termination of the polymerization reaction.
  • the reaction was discontinued, the unreacted monomer in the polymerizer was recovered, and the polymer slurry was then discharged out of the system and dehydrated-and dried to give a PVC resin.
  • the PVC resin obtained had a BET specific surface area value of 0.7 m 2 /g.
  • the ESCA value indicative of the skin layer occurrence extent was 0.2.
  • the void ratio was 5.2% by volume.
  • the PVC resin preparation was made in the same manner as in Example 13 except that a different partially saponified polyvinyl acetate species having an average saponification degree of 76 mole percent and a polymerization degree of 1,000 was used in an amount of 800 ppm and 80 ppm of polyoxyethylene alkyl ether sulfate salt was used in lieu of sorbitan monolaurate.
  • the CPVC resin preparation was made in the same manner as in Example 13.
  • the PVC resin preparation was made in the manner mentioned below.
  • the CPVC resin preparation was made in the same manner as in Example 14.
  • a polymerizer pressure-resistant autoclave; capacity 100 liters was charged with 50 kg of deionized water and 1,000 ppm (on vinyl chloride monomer basis) of partially saponified polyvinyl acetate (average saponification degree 88 mole percent; polymerization degree 1,000) as suspending and dispersing agent, and 550 ppm (on vinyl chloride monomer basis) of tert-butyl peroxyneodecanoate was added. Then, the polymerizer was deaerated to 45 mmHg and, thereafter, 33 kg of vinyl chloride monomer was charged thereinto and stirring was started.
  • the polymerizer was heated to 57° C. to thereby initiate the polymerization and this temperature was maintained until termination of the polymerization reaction.
  • the reaction was discontinued, the unreacted monomer in the polymerizer was recovered, and the polymer slurry was then discharged out of the system and dehydrated and dried to give a PVC resin.
  • the PVC resin obtained had a BET specific surface area value of 0.45 m 2 /g.
  • the ESCA value indicative of the skin layer occurrence extent was 0.16.
  • the void ratio, mean pore size and volume percentage of pores 0.001 to 0.1 ⁇ m in size in the pore size distribution were as shown in Table 1.
  • the PVC resins and CPVC resins obtained in the above examples and comparative examples were measured for BET specific surface area, ESCA peak ratio as well as void ratio, pore size distribution and mean pore size by the measurement methods mentioned above. The results are shown in Table 4.
  • a polymerizer pressure-resistant autoclave; capacity 100 liters
  • 50 kg of deionized water 400 ppm (on vinyl chloride monomer basis; hereinafter same shall apply) of partially saponified polyvinyl acetate (average saponification degree 72 mole percent; polymerization degree 700), 1,600 ppm of sorbitan monolaurate (HLB 8.6), 1,500 ppm of lauricacid, 100ppm of polyacrylamide (Brookfield viscosity of a 0.1% (by weight) aqueous solution at 20° C. and 1 atm.: 51 cps) and 500 ppm of tert-butyl peroxyneodecanoate.
  • partially saponified polyvinyl acetate average saponification degree 72 mole percent; polymerization degree 700
  • 1,600 ppm of sorbitan monolaurate HLB 8.6
  • 1,500 ppm of lauricacid 100ppm of polyacrylamide (Brookfield viscosity of a 0.
  • the polymerizer was deaerated to 45 mmHg and, thereafter, 33 kg of vinyl chloride monomer was charged thereinto and stirring was started.
  • the polymerizer was heated to 57° C. to thereby initiate the polymerization and this temperature was maintained until termination of the polymerization reaction.
  • the reaction was discontinued, the unreacted monomer in the polymerizer was recovered, and the polymer slurry was then discharged out of the system and dehydrated and dried to give a PVC resin.
  • the PVC obtained had a BET specific surface area value of 3.7 m 2 /g.
  • the ESCA value indicative of the skin layer occurrence extent was 0.80.
  • the BET specific surface area and ESCA value were determined by the methods mentioned above.
  • a glass-lined pressure-resistant reactor (capacity 300 liters) was charged with 150 kg of deionized water and 40 kg of the PVC obtained in the above manner, the PVC was dispersed in water by stirring and then the inside air was suctioned by a vacuum pump and the pressure was thereby reduced to a gauge pressure of ⁇ 0.8 kgf/cm 2 .
  • Pressure recovery (recovery to zero (0) gauge pressure) was effected with nitrogen gas and the reactor inside was again suctioned by a vacuum pump to thereby eliminate oxygen from the reactor inside. During this operation, the reactor inside was warmed by passing a heated oil through a jacket.
  • the feeding of chlorine gas was started and the reaction was allowed to proceed at a constant temperature of 110° C.
  • the degree of chlorination was calculated based on the concentration of hydrogen chloride produced in the reactor and, at and from the time point when the degree of chlorination reached 63% by weight, an aqueous solution of hydrogen peroxide with a concentration of 100 ppm was added continuously at a rate of 0.5 kg/hr and the reaction was continued.
  • the degree of chlorination reached 66.5% by weight, the feeding of chlorine gas was discontinued and the chlorination reaction was terminated.
  • the amount of hydrogen peroxide added during the reaction was 4 ppm relative to the amount of the resin charged.
  • the unreacted chlorine was purged by blowing nitrogen gas into the reactor, and the resin obtained was washed with water, dehydrated and dried to give powdery CPVC.
  • the CPVC obtained had a chlorine content of 66.5% by weight.
  • the CPVC obtained was dissolved in tetrahydrofuran and a solution with a concentration of 1 g/kg was prepared. This solution was measured for absorbance at the wavelength 235 nm (cell length 1 cm, measuring temperature 23° C.). The absorbance was 0.13.
  • the CPVC obtained had a void ratio of 34.6% by volume, a specific surface area of 6.4 m 2 /g and a void volume for the range 0.001-0.1 ⁇ m (hereinafter referred to “void volume”) of 7.8% by volume.
  • Example 19 The preparation was made in the same manner as in Example 19 except that the same partially saponified polyvinyl acetate species as used in Example 19 was used in an amount of 550 ppm.
  • the PVC obtained had a BET specific surface area value of 2.1 m 2 /g.
  • the ESCA value indicative of the skin layer occurrence extent was 0.73.
  • the CPVC obtained was dissolved in tetrahydrofuran and a solution with a concentration of 1 g/kg was prepared. This solution was measured for absorbance at the wavelength 235 nm (cell length 1 cm, measuring temperature 23° C.). The absorbance was 0.14.
  • the CPVC obtained had a void ratio of 33.8% by volume, a specific surface area of 5.2 m 2 /g and a void volume of 6.3% by volume.
  • the PVC preparation was made in the same manner as in Example 19.
  • the CPVC preparation was made in the same manner as in Example 19 except that the reaction temperature was 120° C. and that the addition of the aqueous solution of hydrogen peroxide was started when the degree of chlorination reached 65% by weight.
  • the amount of hydrogen peroxide added during the reaction was 2 ppm relative to the charged resin amount.
  • the CPVC obtained was dissolved in tetrahydrofuran and a solution with a concentration of 1 g/kg was prepared. This solution was measured for absorbance at the wavelength 235 nm (cell length 1 cm, measuring temperature 23° C.). The absorbance was 0.11.
  • the CPVC obtained had a void ratio of 32.8% by volume, a specific surface area of 3.5 m 2 /g and a void volume of 4.7% by volume.
  • a polymerizer pressure-resistant autoclave; capacity 100 liters was charged with 50 kg of deionized water and 1,300 ppm (on vinyl chloride monomer basis) of partially saponified polyvinyl acetate (average saponification degree 72 mole percent; polymerization degree 750) as suspending and dispersing agent, and 550 ppm (on vinyl chloride monomer basis) of tert-butyl peroxyneodecanoate was added. Then, the polymerizer was deaerated to 45 mmHg and, thereafter, 33 kg of vinyl chloride monomer was charged thereinto and stirring was started.
  • the polymerizer was heated to 57° C. to thereby initiate the polymerization and this temperature was maintained until termination of the polymerization reaction.
  • the reaction was discontinued, the unreacted monomer in the polymerizer was recovered, and the polymer slurry was then discharged out of the system and dehydrated and dried to give PVC.
  • the PVC obtained had a BET specific surface area value of 0.7 m 2 /g.
  • the ESCA value indicative of the skin layer occurrence extent was 0.20.
  • the CPVC preparation was made in the same manner as in Example 19.
  • the CPVC obtained was dissolved in tetrahydrofuran and a solution with a concentration of 1 g/kg was prepared. This solution was measured for absorbance at the wavelength 235 nm (cell length 1 cm, measuring temperature 23° C.). The absorbance was 0.19.
  • the CPVC obtained had a void ratio of 27.3% by volume, a specific surface area of 1.8 m 2 /g and a void volume of 1.1% by volume.
  • the PVC preparation was made in the same manner as in Example 19.
  • a glass-lined pressure-resistant reactor (capacity 300 liters) was charged with 150 kg of deionized water and 40 kg of the PVC obtained in the above manner, the PVC was dispersed in water by stirring and then the inside air was suctioned by a vacuum pump and the pressure was thereby reduced to a gauge pressure of ⁇ 0.8 kgf/cm 2 . Pressure recovery was effected with nitrogen gas and the reactor inside was again suctioned by a vacuum pump to eliminate oxygen from the reactor inside. During this operation, the reactor inside was warmed by passing a heated oil through a jacket. When the reactor inside temperature reached 70° C., the feeding of chlorine gas was started and the reaction was allowed to proceed at a constant temperature of 85° C.
  • the degree of chlorination was calculated based on the concentration of hydrogen chloride generated in the reactor and, at and from the time point when the degree of chlorination reached 60% by weight, an aqueous solution of hydrogen peroxide with a concentration of 400 ppm was added continuously at a rate of 1.0 kg/hr and the reaction was continued. When the degree of chlorination reached 66.5% by weight, the feeding of chlorine gas was discontinued and the chlorination reaction was terminated. The amount of hydrogen peroxide added during the reaction was 100 ppm relative to the amount of the resin charged.
  • the unreacted chlorine was purged by blowing nitrogen gas into the reactor, and the resin obtained was washed with water, dehydrated and dried to give powdery CPVC.
  • the CPVC obtained had a chlorine content of 66.5% by weight.
  • the CPVC obtained was dissolved in tetrahydrofuran and a solution with a concentration of 1 g/kg was prepared. This solution was measured for absorbance at the wavelength 235 nm (cell length 1 cm, measuring temperature 23° C.). The absorbance was 0.26.
  • the CPVC obtained had a void ratio of 37.2% by volume, a specific surface area of 10.2 m 2 /g and a void volume of 11.7% by volume.
  • the PVC preparation was made in the same manner as in
  • a glass-lined pressure-resistant reactor (capacity 300 liters) was charged with 150 kg of deionized water and 40 kg of the PVC obtained in the above manner, the PVC was dispersed in water by stirring and then the inside air was suctioned by a vacuum pump and the pressure was thereby reduced to a gauge pressure of ⁇ 0.8 kgf/cm 2 . Pressure recovery was effected with nitrogen gas and the reactor inside was again suctioned by a vacuum pump to eliminate oxygen from the reactor inside. During this operation, the reactor inside was warmed by passing a heated oil through a jacket. When the reactor inside temperature reached 90° C., the feeding of chlorine gas was started and the reaction was allowed to proceed at a constant temperature of 140° C. The degree of chlorination was calculated based on the concentration of hydrogen chloride generated in the reactor and, at and from the time point when the degree of chlorination reached 66.5% by weight, the feeding of chlorine gas was discontinued and the chlorination reaction was terminated.
  • the unreacted chlorine was purged by blowing nitrogen gas into the reactor, and the resin obtained was washed with water, dehydrated and dried to give powdery CPVC.
  • the CPVC obtained had a chlorine content of 66.5% by weight.
  • the CPVC obtained was dissolved in tetrahydrofuran and a solution with a concentration of 1 g/kg was prepared. This solution was measured for absorbance at the wavelength 235 nm (cell length 1 cm, measuring temperature 23° C.). The absorbance was 0.41.
  • the CPVC obtained had a void ratio of 28.8% by volume, a specific surface area of 1.9 m 2 /g and a void volume of 1.3% by volume.
  • the PVC preparation was made in the same manner as in Example 19.
  • a titanium-made reactor for photochlorination (capacity 300 liters) was charged with 150 kg of deionized water and 40 kg of the PVC obtained in the above manner, the PVC was dispersed in water by stirring and then the inside air was suctioned by a vacuum pump and the pressure was thereby reduced to a gauge pressure of ⁇ 0.8 kgf/cm 2 . Pressure recovery was effected with nitrogen gas and the reactor inside was again suctioned by a vacuum pump to eliminate oxygen from the reactor inside. During this operation, the reactor inside was warmed by passing a heated oil through a jacket. When the reactor inside temperature reached 70° C., the feeding of chlorine gas was started and the reaction was allowed to proceed at 70° C.
  • the degree of chlorination was calculated based on the concentration of hydrogen chloride generated in the reactor and, at and from the time point when the degree of chlorination reached 66.5% by weight, the feeding of chlorine gas was discontinued and the chlorination reaction was terminated.
  • the unreacted chlorine was purged by blowing nitrogen gas into the reactor, and the resin obtained was washed with water, dehydrated and dried to give powdery CPVC.
  • the CPVC obtained had a chlorine content of 66.5% by weight.
  • the CPVC obtained was dissolved in tetrahydrofuran and a solution with a concentration of 1 g/kg was prepared. This solution was measured for absorbance at the wavelength 235 nm (cell length 1 cm, measuring temperature 23° C.). The absorbance was 0.38.
  • the CPVC obtained had a void ratio of 37.8% by volume, a specific surface area of 11.5 m 2 /g and a void volume of 12.2% by volume.
  • the PVC preparation and CPVC preparation were made in the same manner as in Example 21.
  • the CPVC obtained was dissolved in tetrahydrofuran and subjected to methanol precipitation evaluation.
  • the addition amount Y at the time of initiation of precipitation was 42 g
  • the amount Z at the time of 80% precipitation was 55 g.
  • the CPVC obtained had a void ratio of 32.8% by volume, a specific surface area of 3.5 m 2 /g, and a void volume of 4.7% by volume.
  • the PVC preparation was made in the same manner as in Example 22.
  • the preparation was made in the same manner as in Example 22 except that the chlorine content was raised to 68.0% by weight and that the amount of hydrogen peroxide added during the reaction was 8 ppm relative to the charged resin amount.
  • the CPVC obtained was dissolved in tetrahydrofuran and subjected to methanol precipitation evaluation. As a result, the addition amount Y at the time of initiation of precipitation was 36 g, and the amount Z at the time of 80% precipitation was 49 g.
  • the CPVC obtained had a void ratio of 33.5% by volume, a specific surface area of 4.7 m 2 /g, and a void volume of 5.8% by volume.
  • the PVC preparation was made in the same manner as in Example 22.
  • the preparation was made in the same manner as in Example 22 except that the reaction temperature was 130° C. and that the addition of the aqueous solution of hydrogen peroxide was omitted.
  • the CPVC obtained was dissolved in tetrahydrofuran and subjected to methanol precipitation evaluation. As a result, the addition amount Y at the time of initiation of precipitation was 44 g, and the amount Z at the time of 80% precipitation was 52 g.
  • the CPVC obtained had a void ratio of 30.9% by volume, a specific surface area of 2.5 m 2 /g, and a void volume of 2.9% by volume.
  • the PVC preparation was made in the same manner as in Example 22.
  • a glass-lined pressure-resistant reactor (capacity 300 liters) was charged with 150 kg of deionized water and 40 kg of the PVC obtained in the above manner, the PVC was dispersed in water by stirring and then the inside air was suctioned by a vacuum pump and the pressure was thereby reduced to a gauge pressure of ⁇ 0.8 kgf/cm 2 . Pressure recovery was effected with nitrogen gas and the reactor inside was again suctioned by a vacuum pump to eliminate oxygen from the reactor inside. During this operation, the reactor inside was warmed by passing a heated oil through a jacket.
  • the feeding of chlorine gas was started and the reaction was allowed to proceed at a constant temperature of 100° C.
  • the degree of chlorination was calculated based on the concentration of hydrogen chloride generated in the reactor and, at and from the time point when the degree of chlorination reached 62% by weight, an aqueous solution of hydrogen peroxide with a concentration of 100 ppm was added continuously at a rate of 0.5 kg/hr and the reaction was continued.
  • the degree of chlorination reached 66.5% by weight, the feeding of chlorine gas was discontinued and the chlorination reaction was terminated.
  • the amount of hydrogen peroxide added during the reaction was 10 ppm relative to the amount of the resin charged.
  • the unreacted chlorine was purged by blowing nitrogen gas into the reactor, and the resin obtained was washed with water, dehydrated and dried to give powdery CPVC.
  • the CPVC obtained had a chlorine content of 66.5% by weight.
  • the CPVC obtained was dissolved in tetrahydrofuran and subjected to methanol precipitation evaluation. As a result, the addition amount Y at the time of initiation of precipitation was 35 g, and the amount Z at the time of 80% precipitation was 62 g.
  • the CPVC obtained had a void ratio of 35.2% by volume, a specific surface area of 8.3 m 2 /g, and a void volume of 9.2% by volume.
  • the CPVC obtained was dissolved in tetrahydrofuran and subjected to methanol precipitation evaluation. As a result, the addition amount Y at the time of initiation of precipitation was 46 g, and the amount Z at the time of 80% precipitation was 51 g.
  • the CPVC obtained had a void ratio of 28.8% by volume, a specific surface area of 1.9 m 2 /g, and a void volume of 1.3% by volume.
  • the PVC preparation was made in the same manner as in Example 22.
  • a titanium-made reactor for photochlorination (capacity 300 liters) was charged with 150 kg of deionized water and 40 kg of the PVC obtained in the above manner, the PVC was dispersed in water by stirring and then the inside air was suctioned by a vacuum pump and the pressure was thereby reduced to a gauge pressure of ⁇ 0.8 kgf/cm 2 . Pressure recovery was effected with nitrogen gas and the reactor inside was again suctioned by a vacuum pump to eliminate oxygen from the reactor inside. During this operation, the reactor inside was warmed by passing a heated oil through a jacket. When the reactor inside temperature reached 70° C., the feeding of chlorine gas was started and the reaction was allowed to proceed at 70° C. under irradiation by a high pressure mercury lamp. The degree of chlorination was calculated based on the concentration of hydrogen chloride generated in the reactor and, at and from the time point when the degree of chlorination reached 68.0% by weight, the feeding of chlorine gas was discontinued and the chlorination reaction was terminated.
  • the unreacted chlorine was purged by blowing nitrogen gas into the reactor, and the resin obtained was washed with water, dehydrated and dried to give powdery CPVC.
  • the CPVC obtained had a chlorine content of 68.0% by weight.
  • the CPVC obtained was dissolved in tetrahydrofuran and subjected to methanol precipitation evaluation. As a result, the addition amount Y at the time of initiation of precipitation was 25 g, and the amount Z at the time of 80% precipitation was 60 g.
  • the CPVC obtained had a void ratio of 38.5% by volume, a specific surface area of 11.8 m 2 /g, and a void volume of 13.6% by volume.
  • the PVC preparation was made in the same manner as in Comparative Example 11.
  • the CPVC preparation was made in the same manner as in Example 22.
  • a polymerizer pressure-resistant autoclave; capacity 100 liters
  • 50 kg of deionized water 400 ppm (on vinyl chloride monomer basis; hereinafter same shall apply) of partially saponified polyvinyl acetate (average saponification degree 72 mole percent; polymerization degree 700), 1,600 ppm of sorbitan monolaurate (HLB 8.6), 1,500 ppm of lauric acid, 100 ppm of polyacrylamide (Brookfield viscosity of a 0.1% (by weight) aqueous solution at 20° C. and 1 atm.: 51 cps) and 500 ppm of tert-butyl peroxyneodecanoate.
  • the polymerizer was deaerated to 45 mmHg and, thereafter, 33 kg of vinyl chloride monomer was charged thereinto and stirring was started.
  • the polymerizer was heated to 57° C to thereby initiate the polymerization and this temperature was maintained until termination of the polymerization reaction.
  • the reaction was discontinued, the unreacted monomer in the polymerizer was recovered, and the polymer slurry was then discharged out of the system and dehydrated and dried to give PVC.
  • the PVC obtained had a BET specific surface area value of 3.7 m 2 /g.
  • the ESCA value indicative of the skin layer occurrence extent was 0.80.
  • the BET specific surface area and ESCA value were determined by the methods mentioned herein.
  • a glass-lined pressure-resistant reactor (capacity 300 liters) was charged with 150 kg of deionized water and 40 kg of the PVC obtained in the above manner, the PVC was dispersed in water by stirring and then the inside air was suctioned by a vacuum pump and the pressure was thereby reduced to a gauge pressure of ⁇ 0.8 kgf/cm 2 .
  • Pressure recovery (recovery to zero (0) gauge pressure) was effected with nitrogen gas and the reactor inside was again suctioned by a vacuum pump to thereby eliminate oxygen from the reactor inside. During this operation, the reactor inside was warmed by passing a heated oil through a jacket.
  • the feeding of chlorine gas was started and the reaction was allowed to proceed at a constant temperature of 110° C.
  • the degree of chlorination was calculated based on the concentration of hydrogen chloride produced in the reactor and, at and from the time point when the degree of chlorination reached 63% by weight, an aqueous solution of hydrogen peroxide with a concentration of 100 ppm was added continuously at a rate of 0.5 kg/hr and the reaction was continued.
  • the degree of chlorination reached 66.5% by weight, the feeding of chlorine gas was discontinued and the chlorination reaction was terminated.
  • the amount of hydrogen peroxide added during the reaction was 4 ppm relative to the amount of the resin charged.
  • the unreacted chlorine was purged by blowing nitrogen gas into the reactor, and the resin obtained was washed with water, dehydrated and dried to give powdery CPVC.
  • the CPVC obtained had a chlorine content of 66.5% by weight.
  • the CPVC obtained had a void ratio of 34.6% by volume, a specific surface area of 6.4 m 2 /g and a void volume for the range 0.001 to 0.1 ⁇ m (hereinafter referred to “void volume”) of 7.8% by volume.
  • the PVC preparation was made in the same manner as in Example 26.
  • a glass-lined pressure-resistant reactor (capacity 300 liters) was charged with 150 kg of deionized water and 40 kg of the PVC obtained in the above manner, the PVC was dispersed in water by stirring and then the inside air was suctioned by a vacuum pump and the pressure was thereby reduced to a gauge pressure of ⁇ 0.8 kgf/cm 2 . Pressure recovery was effected with nitrogen gas and the reactor inside was again suctioned by a vacuum pump to thereby eliminate oxygen from the reactor inside. During this operation, the reactor inside was warmed by passing a heated oil through a jacket.
  • the reaction was allowed to proceed while the reactor inside was irradiated with ultraviolet rays using a mercury lamp.
  • the degree of chlorination was calculated based on the concentration of hydrogen chloride generated in the reactor and, when the degree of chlorination reached 66.5% by weight, the chlorination reaction was terminated.
  • the unreacted chlorine was purged by blowing nitrogen gas into the reactor, and the resin obtained was washed with water, dehydrated and dried to give powdery CPVC.
  • the CPVC obtained had a chlorine content of 66.5% by weight.
  • the CPVC obtained had a void ratio of 35.2% by volume, a specific surface area of 6.6 m 2 /g and a void volume of 8.1% by volume.
  • the PVC preparation was made in the same manner as in Example 26.
  • a glass-lined pressure-resistant reactor (capacity 300 liters) was charged with 150 kg of deionized water and 40 kg of the PVC obtained in the above manner, the PVC was dispersed in water by stirring and then the inside air was suctioned by a vacuum pump and the pressure was thereby reduced to a gauge pressure of ⁇ 0.8 kgf/cm 2 . Pressure recovery was effected with nitrogen gas and the reactor inside was again suctioned by a vacuum pump to thereby eliminate oxygen from the reactor inside. During this operation, the reactor inside was warmed by passing a heated oil through a jacket.
  • the feeding of chlorine gas was started and the reaction was allowed to proceed at a constant temperature of 90° C.
  • the degree of chlorination was calculated based on the concentration of hydrogen chloride generated in the reactor and, at and after the degree of chlorination reached 62% by weight, an aqueous solution of hydrogen peroxide with a concentration of 100 ppm was added continuously at a rate of 0.5 kg/hr, and the reaction was continued.
  • the degree of chlorination reached 66.5% by weight, the feeding of chlorine gas was discontinued and the chlorination reaction was terminated.
  • the amount of hydrogen peroxide added during the reaction was 8 ppm relative to the charged resin amount.
  • the CPVC obtained had a void ratio of 35.0% by volume, a specific surface area of 6.6 m 2 /g and a void volume of 8.0% by volume.
  • the PVC preparation was made in the same manner as in Example 26.
  • the CPVC preparation was made in the same manner as in Example 26 except that the reaction temperature was 130° C. and that the addition of hydrogen peroxide was omitted.
  • the unreacted chlorine was purged by blowing nitrogen gas into the reactor, and the resin obtained was washed with water, dehydrated and dried to give powdery CPVC.
  • the CPVC obtained had a chlorine content of 66.5% by weight.
  • the CPVC obtained had a void ratio of 33.9% by volume, a specific surface area of 6.1 m 2 /g and a void volume of 7.6% by volume.
  • the PVC preparation was made in the same manner as in Example 26 except that the partially saponified polyvinyl acetate used in Example 26 was used in an amount of 550 ppm.
  • the CPVC preparation was made in the same manner as in Example 26.
  • the CPVC obtained had a void ratio of 33.8% by volume, a specific surface area of 5.2 m 2 /g and a void volume of 6.3% by volume.
  • the PVC preparation was made in the same manner as in Example 26.
  • the CPVC preparation was made in the same manner as in Example 26 except that the degree of chlorination of CPVC was made 64.0% by weight and that the addition of hydrogen peroxide was omitted.
  • the CPVC obtained had a void ratio of 34.1% by volume, a specific surface area of 6.3 m 2 /g and a void volume of 7.6% by volume.
  • the PVC preparation was made in the same manner as in Example 26.
  • the CPVC preparation was made in the same manner as in Example 26 except that the degree of chlorination of CPVC was made 70.0% by weight.
  • the amount of hydrogen peroxide added was 10 ppm relative to the charged resin amount.
  • the CPVC obtained had a void ratio of 35.3% by volume, a specific surface area of 6.7 m 2 /g and a void volume of 8.1% by volume.
  • a polymerizer pressure-resistant autoclave; capacity 100 liters was charged with 50 kg of deionized water and 1,300 ppm (on vinyl chloride monomer basis) of partially saponified polyvinyl acetate (average saponification degree 72 mole percent; polymerization degree 750) as suspending and dispersing agent, and 550 ppm (on vinyl chloride monomer basis) of tert-butyl peroxyneodecanoate was added. Then, the polymerizer was deaerated to 45 mmHg and, thereafter, 33 kg of vinyl chloride monomer was charged thereinto and stirring was started. The polymerizer was heated to 57° C. to thereby initiate the polymerization and this temperature was maintained until termination of the polymerization reaction.
  • the reaction was discontinued, the unreacted monomer in the polymerizer was recovered, and the polymer slurry was then discharged out of the system and dehydrated and dried to give PVC.
  • the PVC obtained had a BET specific surface area value of 3.7 m 2 /g.
  • the ESCA value indicative of the'skin layer occurrence extent was 0.80.
  • the BET specific surface area measurement and ESCA were carried out by the method described herein.
  • the CPVC preparation was made in the same manner as in Example 26.
  • the CPVC obtained had a void ratio of 27.3% by volume, a specific surface area of 1.8 m 2 /g and a void volume of 1.1% by volume.
  • the PVC preparation was made in the same manner as in Comparative Example 18.
  • the CPVC preparation was made in the same manner as in Example 27.
  • the CPVC obtained had a void ratio of 27.9% by volume, a specific surface area of 2.0 m2/g and a void volume of 1.4% by volume.
  • the PVC preparation was made in the same manner as in Example 26.
  • the CPVC preparation was made in the same manner as in. Example 26 except that the reaction temperature was 140° C. and that the addition of hydrogen peroxide was omitted.
  • the CPVC obtained had a void ratio of 28.8% by volume, a specific surface area of 1.9 m 2 /g and a void volume of 1.3% by volume.
  • the PVC preparation was made in the same manner as in Example 26.
  • the CPVC preparation was made in the same manner as in Example 26 except that the degree of chlorination of CPVC was made 73.0% by weight.
  • the amount of hydrogen peroxide added was 40 ppm relative to the charged resin amount.
  • the CPVC obtained had a void ratio of 36.8% by volume, a specific surface area of 10.0 m 2 /g and a void volume of 12.1% by volume.
  • the CPVC obtained was dissolved in tetrahydrofuran and a solution with a concentration of 1 g/kg was prepared. This solution was measured for absorbance at the wavelength 235 nm (cell length 1 cm, measuring temperature 23° C.) The absorbance was 0.13.
  • the PVC preparation was made in the same manner as in Example 26.
  • the CPVC preparation was made in the same manner as in Example 27.
  • the CPVC obtained was dissolved in tetrahydrofuran and a solution with a concentration of 1 g/kg was prepared. This solution was measured for absorbance at the wavelength 235 nm (cell length 1 cm, measuring temperature 23° C.). The absorbance was 0.70.
  • the PVC preparation was made in the same manner as in Example 26.
  • the CPVC preparation was made in the same manner as in Example 28.
  • the CPVC obtained was dissolved in tetrahydrofuran and a solution with a concentration of 1 g/kg was prepared. This solution was measured for absorbance at the wavelength 235 nm (cell length 1 cm, measuring temperature 23° C.). The absorbance was 0.12.
  • the PVC preparation was made in the same manner as in Example 26.
  • the CPVC obtained was dissolved in tetrahydrofuran and a solution with a concentration of 1 g/kg was prepared. This solution was measured for absorbance at the wavelength 235 nm (cell length 1 cm, measuring temperature 23° C.) The absorbance was 0.32.
  • the CPVC obtained was dissolved in tetrahydrofuran and a solution with a concentration of 1 g/kg was prepared. This solution was measured for absorbance at the wavelength 235 nm (cell length 1 cm, measuring temperature 23° C.). The absorbance was 0.14.
  • the PVC preparation was made in the same manner as in Example 26.
  • the CPVC preparation was made in the same manner as in Example 31.
  • the CPVC obtained was dissolved in tetrahydrofuran and a solution with a concentration of 1 g/kg was prepared. This solution was measured for absorbance at the wavelength 235 nm (cell length 1 cm, measuring temperature 23° C.). The absorbance was 0.10.
  • the PVC preparation was made in the same manner as in Example 26.
  • the CPVC preparation was made in the same manner as in Example 32.
  • the CPVC obtained was dissolved in tetrahydrofuran and a solution with a concentration of 1 g/kg was prepared. This solution was measured for absorbance at the wavelength 235 nm (cell length 1 cm, measuring temperature 23° C.) The absorbance was 0.29.
  • the CPVC obtained was dissolved in tetrahydrofuran and a solution with a concentration of 1 g/kg was prepared. This solution was measured for absorbance at the wavelength 235 nm (cell length 1 cm, measuring temperature 23° C.). The absorbance was 0.27.
  • the PVC preparation was made in the same manner as in Comparative Example 18.
  • the CPVC preparation was made in the same manner as in Comparative Example 19.
  • the CPVC obtained was dissolved in tetrahydrofuran and a solution with a concentration of 1 g/kg was prepared. This solution was measured for absorbance at the wavelength 235 nm (cell length 1 cm, measuring temperature 23° C.). The absorbance was 0.85.
  • the PVC preparation was made in the same manner as in Example 26.
  • a glass-lined pressure-resistant reactor (capacity 300 liters) was charged with 150 kg of deionized water and 40 kg of the PVC obtained in the above manner, the PVC was dispersed in water by stirring and then the inside air was suctioned by a vacuum pump and the pressure was thereby reduced to a gauge pressure of ⁇ 0.8 kgf/cm 2 . Pressure recovery was effected with nitrogen gas and the reactor inside was again suctioned by a vacuum pump to eliminate oxygen from the reactor inside. During this operation, the reactor inside was warmed by passing a heated oil through a jacket.
  • the feeding of chlorine gas was started and the reaction was allowed to proceed at a constant temperature of 65° C.
  • the degree of chlorination was calculated based on the concentration of hydrogen chloride generated in the reactor and, at and from the time point when the degree of chlorination reached 63% by weight, an aqueous solution of hydrogen peroxide with a concentration of 500 ppm was added continuously at a rate of 0.5 kg/hr and the reaction was continued.
  • the degree of chlorination reached 66.5% by weight, the feeding of chlorine gas was discontinued and the chlorination reaction was terminated.
  • the amount of hydrogen peroxide added during the reaction was 500 ppm relative to the amount of the resin charged.
  • the unreacted chlorine was purged by blowing nitrogen gas into the reactor, and the resin obtained was washed with water, dehydrated and dried to give powdery CPVC.
  • the CPVC obtained had a chlorine content of 66.5% by weight.
  • the CPVC obtained was dissolved in tetrahydrofuran and a solution with a concentration of 1 g/kg was prepared. This solution was measured for absorbance at the wavelength 235 nm (cell length 1 cm, measuring temperature 23C). The absorbance was 1.32.
  • the CPVC obtained had a void ratio of 35.9% by volume, a specific surface area value of 6.9 m 2 /g and a void volume of 8.3% by volume.
  • the PVC preparation was made in the same manner as in Example 26.
  • the CPVC preparation was made in the same manner as in Example 27 except that the reaction temperature was 60° C.
  • the CPVC preparation was made in the same manner as in Comparative Example 20.
  • the CPVC obtained was dissolved in tetrahydrofuran and a solution with a concentration of 1 g/kg was prepared. This solution was measured for absorbance at the wavelength 235 nm (cell length 1 cm, measuring temperature 23° C.). The absorbance was 0.41.
  • the PVC preparation was made in the same manner as in Example 26.
  • the polymerizer was deaerated to 45 mmHg and, thereafter, 33 kg of vinyl chloride monomer was charged thereinto and stirring was started.
  • the polymerizer was heated to 57° C. to thereby initiate the polymerization and this temperature was maintained until termination of the polymerization reaction.
  • the reaction was discontinued, the unreacted monomer in the polymerizer was recovered, and the polymer slurry was then discharged out of the system and dehydrated and dried to give PVC.
  • the PVC obtained had a BET specific surface area value of 3.7 m 2 /g.
  • the ESCA value indicative of the skin layer occurrence extent was 0.80.
  • the BET specific surface area and ESCA value were determined by the methods mentioned herein.
  • a glass-lined pressure-resistant reactor (capacity 300 liters) was charged with 150 kg of deionized water and 40 kg of the PVC obtained in the above manner, the PVC was dispersed in water by stirring and then the inside air was suctioned by a vacuum pump and the pressure was thereby reduced to a gauge pressure of ⁇ 0.8 kgf/cm 2 .
  • Pressure recovery (recovery to zero (0) gauge pressure) was effected with nitrogen gas and the reactor inside was again suctioned by a vacuum pump to thereby eliminate oxygen from the reactor inside. During this operation, the reactor inside was warmed by passing a heated oil through a jacket.
  • the PVC preparation was made in the same manner as in Example 1 except that the partially saponified polyvinyl acetate was used in an amount of 550 ppm.
  • the CPVC preparation was made in the same manner as in Example 40.
  • the CPVC obtained had a void ratio of 33.8% by volume, a specific surface area of 6.2 m 2 /g and a void volume of 7.1% by volume.
  • the ESCA value was 0.52.
  • the PVC preparation was made in the same manner as in Example 40.
  • the CPVC preparation was made in the same manner as in Example 40 except that the reaction temperature was 130° C.
  • the amount of hydrogen peroxide added during the reaction was 15 ppm relative to the amount of the resin charged.
  • the CPVC obtained had a void ratio of 34.1% by volume, a specific surface area of 5.8 m 2 /g and a void volume of 6.2% by volume.
  • the ESCA value was 0.68.
  • the PVC preparation was made in the same manner as in Example 41.
  • the CPVC preparation was made in the same manner as in Example 40 except that the final degree of chlorination was 75.7% by weight.
  • the amount of hydrogen peroxide added during the reaction was 50 ppm relative to the amount of the resin charged.
  • the CPVC obtained had a void ratio of 34.7% by volume, a specific surface area of 7.3 m 2 /g and a void volume of 8.3% by volume.
  • the ESCA value was 0.61.
  • a polymerizer pressure-resistant autoclave; capacity 100 liters was charged with 50 kg of deionized water and 1,300 ppm (on vinyl chloride monomer basis) of partially saponified polyvinyl acetate (average saponification degree 72 mole percent; polymerization degree 750) as suspending and dispersing agent, and 550 ppm (on vinyl chloride monomer basis) of tert-butyl peroxyneodecanoate was added. Then, the polymerizer was deaerated to 45 mmHg and, thereafter, 3.3 kg of vinyl chloride monomer was charged thereinto and stirring was started. The polymerizer was heated to 57° C. to thereby initiate the polymerization and this temperature was maintained until termination of the polymerization reaction.
  • the reaction was discontinued, the unreacted monomer in the polymerizer was recovered, and the polymer slurry was then discharged out of the system and dehydrated and dried to give PVC.
  • the PVC obtained had a BET specific surface area value of 0.7 m 2 /g.
  • the ESCA value indicative of the skin layer occurrence extent was 0.20.
  • the BET specific surface area measurement and ESCA were carried out by the method described herein.
  • the CPVC preparation was made in the same manner as in Example 40.
  • the CPVC obtained had a void ratio of 28.2% by volume, a specific surface area of 2.3 m 2 /g and a void volume of 1.7% by volume.
  • the ESCA value was 0.15.
  • the PVC preparation was made in the same manner as in Example 40.
  • the CPVC preparation was made in the same manner as in Example 40 except that the reaction temperature was 137° C. and that the addition of hydrogen peroxide was omitted.
  • the CPVC obtained had a void ratio of 29.5% by volume, a specific surface area of 2.6 m 2 /g and a void volume of 1.8%, by volume.
  • the ESCA value was 0.64.
  • the PVC preparation was made in the same manner as in Example 41.
  • the CPVC preparation was made in the same manner as in Example 40 except that the final degree of chlorination was 70.5% by weight.
  • the amount of hydrogen peroxide added during the reaction was 16 ppm relative to the amount of the resin charged.
  • the CPVC obtained had a void ratio of 35.9% by volume, a specific surface area of 8.4 m 2 /g and a void volume of 10.8% by volume.
  • the ESCA value was 0.68.
  • a polymerizer pressure-resistant autoclave; capacity 100 liters
  • 50 kg of deionized water 400 ppm (on vinyl chloride monomer basis; hereinafter same shall apply) of partially saponified polyvinyl acetate (average saponification degree 72 mole percent; polymerization degree 700), 1,600 ppm of sorbitan monolaurate (HLB 8.6), 1,500 ppm of lauric acid, 100 ppm of polyacrylamide (Brookfield viscosity of a 0.1% (by weight) aqueous solution at 20° C. and 1 atm.: 51 cps) and 500 ppm of tert-butyl peroxyneodecanoate.
  • the polymerizer was deaerated to 45 mmHg and, thereafter, 33 kg of vinyl chloride monomer was charged thereinto and stirring was started.
  • the polymerizer was heated to 57° C. to thereby initiate the polymerization and this temperature was maintained until termination of the polymerization reaction.
  • a glass-lined pressure-resistant reactor (capacity 300 liters) was charged with 150 kg of deionized water and 40 kg of the PVC obtained in the above manner, the PVC was dispersed in water by stirring and then the inside air was suctioned by a vacuum pump and the pressure was thereby reduced to a gauge pressure of ⁇ 0.8 kgf/cm 2 .
  • Pressure recovery (recovery to zero (0) gauge pressure) was effected with nitrogen gas and the reactor inside was again suctioned by a vacuum pump to thereby eliminate oxygen from the reactor inside. During this operation, the reactor inside was warmed by passing a heated oil through a jacket.
  • the CPVC obtained had a chlorination degree of 70.5% by weight, a void ratio of 35.9% by volume, a specific surface area of 8.4 m 2 /g, a void volume for the range 0.001 to 0.1 ⁇ m (hereinafter referred to “void volume”) of 10.8% by volume and an ESCA value of 0.68.
  • the additives specified in Table 10 were added to 100 parts by weight of the above CPVC and the whole was blended with heating in a Henschel mixer.
  • Resin temperature 215 to 217° C.
  • Barrel temperature 185 to 210° C.
  • Mold temperature 200 to 215° C.
  • the PVC preparation was made in the same manner as in Example 44.
  • the CPVC preparation was made in the same manner as in Example 1 except that the reaction temperature was 120° C. and that the addition of hydrogen peroxide was started at the time of 65.0% by weight of chlorination.
  • the CPVC obtained had a chlorination degree of 70.5% by weight, a void ratio of 32.1% by volume, a specific surface area of 4.6 m 2 /g, a void volume of 5.2% by volume and an ESCA value of 0.63.
  • the PVC preparation was made in the same manner as in Example 44.
  • the CPVC preparation was made in the same manner as in Example 44 except that the final degree of chlorination was 69.0% by weight.
  • the CPVC obtained had a chlorination degree of 69.0% by weight, a void ratio of 35.0% by volume, a specific surface area of 7.3 m 2 /g, a void volume of 8.1% by volume and an ESCA value of 0.64.
  • the PVC preparation was made in the same manner as in Example 44.
  • the CPVC preparation was made in the same manner as in Example 44 except that the final degree of chlorination was 72.1% by weight.
  • the CPVC obtained had a chlorination degree of 72.1% by weight, a void ratio of 36.4% by volume, a specific surface area of 9.7 m 2 /g, a void volume of 11.6% by volume and an ESCA value of 0.70.
  • the compounding and molding were carried out in the same manner as in Example 44 except that the resin temperature was 220 to 223° C.
  • the PVC preparation was made in the same manner as in Example 44.
  • the CPVC preparation was made in the same manner as in Example 45 except that the final degree of chlorination was 72.1% by weight.
  • the CPVC obtained had a chlorination degree of 72.1% by weight, a void ratio of 32.6% by volume, a specific surface area of 5.7 m 2 /g, a void volume of 6.5% by volume and an ESCA value of 0.66.
  • the PVC preparation was made in the same manner as in Example 44.
  • the CPVC preparation was made in the same manner as in Example 44 except that the final degree of chlorination was 71.5% by weight.
  • the CPVC obtained had a chlorination degree of 71.5% by weight, a void ratio of 36.1% by volume, a specific surface area of 8.7 m 2 /g, a void volume of 11.1% by volume and an ESCA value of 0.69.
  • the PVC preparation was made in the same manner as in Example 44.
  • the CPVC preparation was made in the same manner as in Example 44 except that the final degree of chlorination was 74.6% by weight.
  • the CPVC obtained had a chlorination degree of 74.6% by weight, a void ratio of 37.7% by volume, a specific surface area of 10.3 m 2 /g, a void volume of 11.9% by volume and an ESCA value of 0.74.
  • the compounding was carried out in the same manner as in Example 44 except that the organotin stabilizer was used in an amount of 2.5 phr.
  • the molding was carried out in the same manner as in Example 44 except that the resin temperature was 225 ⁇ 228° C.
  • the PVC preparation was made in the same manner as in Example 44.
  • the CPVC preparation was made in the same manner as in Example 45 except that the final degree of chlorination was 74.6% by weight.
  • the CPVC obtained had a chlorination degree of 74.6% by weight, a void ratio of 33.8% by volume, a specific surface area of 6.9 m 2 /g, a void volume of 7.7% by volume and an ESCA value of 0.70.
  • the PVC preparation was made in the same manner as in Example 44.
  • the CPVC preparation was made in the same manner as in Example 44 except that the final degree of chlorination was 73.5% by weight.
  • the CPVC obtained had a chlorination degree of 73.5% by weight, a void ratio of 37.0% by volume, a specific surface area of 10.1 m 2 /g, a void volume of 11.7% by volume and an ESCA value of 0.72.
  • the CPVC obtained had a chlorination degree of 70.5% by weight, a void ratio of 35.9% by volume, a specific surface area of 8.4 m 2 /g, a void volume of 10.8% by volume and an ESCA value of 0.68.
  • the PVC preparation was made in the same manner as in Example 44.
  • the CPVC preparation was made in the same manner as in Example 45.
  • the CPVC obtained had a chlorination degree of 70.5% by weight, a void ratio of 32.1% by volume, a specific surface area of 4.6 m 2 /g, a void volume of 5.2% by volume and an ESCA value of 0.63.
  • a polymerizer pressure-resistant autoclave; capacity 100 liters was charged with 50 kg of deionized water and 1,300 ppm (on vinyl chloride monomer basis) of partially saponified polyvinyl acetate (average saponification degree 72 mole percent; polymerization degree 750) as suspending and dispersing agent, and 550 ppm (on vinyl chloride monomer basis) of tert-butyl peroxyneodecanoate was added. Then, the polymerizer was deaerated to 45 mmHg and, thereafter, 33 kg of vinyl chloride monomer was charged thereinto and stirring was started. The polymerizer was heated to 57° C. to thereby initiate the polymerization and this temperature was maintained until termination of the polymerization reaction. When the conversion by polymerization reached 90%, the reaction was discontinued, the unreacted monomer in the polymerizer was recovered, and the polymer slurry was then discharged out of the system and dehydrated and dried to give PVC.
  • the CPVC preparation was made in the same manner as in Example 44.
  • the CPVC obtained had a chlorination degree of 70.5% by weight, a void ratio of 27.3% by volume, a specific surface area value of 1.7 m 2 /g, a void volume of 1.2% by volume and an ESCA value of 0.15.
  • the PVC preparation was made in the same manner as in Example 44.
  • a glass-lined pressure-resistant reactor (capacity 300 liters) was charged with 150 kg of deionized water and 40 kg of the PVC obtained in the above manner, the PVC was dispersed in water by stirring and then the inside air was suctioned by a vacuum pump and the pressure was thereby reduced to a gauge pressure of ⁇ 0.8 kgf/cm 2 . Pressure recovery was effected with nitrogen gas and the reactor inside was again suctioned by a vacuum pump to thereby eliminate oxygen from the reactor inside. During this operation, the reactor inside was warmed by passing a heated oil through a jacket. When the reactor inside temperature reached 90° C., the feeding of chlorine gas was started and the reaction was allowed to proceed at a constant temperature of 140° C. The degree of chlorination was calculated based on the concentration of hydrogen chloride produced in the reactor and, at the time point when the degree of chlorination was confirmed to have reached 70.5% by weight, the feeding of chlorine gas was discontinued and the chlorination reaction was terminated.
  • the CPVC obtained had a chlorination degree of 70.5% by weight, a void ratio of 27.9% by volume, a specific surface area of 1.8 m 2 /g, a void volume of 1.1% by volume and an ESCA value of 0.42.
  • the CPVC obtained had a chlorination degree of 69.0% by weight, a void ratio of 35.0% by volume, a specific surface area of 7.3 m 2 /g, a void volume of 8.1% by volume and an ESCA value of 0.64.
  • the PVC preparation was made in the same manner as in Example 44.
  • the CPVC preparation was made in the same manner as in Example 46.
  • the CPVC obtained had a chlorination degree of 72.1% by weight, a void ratio of 36.4% by volume, a specific surface area of 9.7 m 2 /g, a void volume of 11.6% by volume and an ESCA value of 0.70.
  • the PVC preparation was made in the same manner as in Example 44.
  • the CPVC preparation was made in the same manner as in Example 47.
  • the CPVC obtained had a chlorination degree of 72.1% by weight, a void ratio of 32.6% by volume, a specific surface area of 5.7 m 2 /g, a void volume of 6.5% by volume and an ESCA value of 0.66.
  • the PVC preparation was made in the same manner as in Example 44.
  • a glass-lined pressure-resistant reactor (capacity 300 liters) was charged with 150 kg of deionized water and 40 kg of the PVC obtained in the above manner, the PVC was dispersed in water by stirring and then the inside air was suctioned by a vacuum pump and the pressure was thereby reduced to a gauge pressure of ⁇ 0.8 kgf/cm 2 . Pressure recovery was effected with nitrogen gas and the reactor inside was again suctioned by a vacuum pump to thereby eliminate oxygen from the reactor inside. During this operation, the reactor inside was warmed by passing a heated oil through a jacket.
  • the CPVC obtained had a chlorination degree of 72.1% by weight, a void ratio of 29.5% by volume, a specific surface area of 2.6 m 2 /g, a void volume of 1.8% by volume and an ESCA value of 0.64.
  • the CPVC obtained had a chlorination degree of 71.5% by weight, a void ratio of 36.1% by volume, a specific surface area of 8.7 m 2 /g, a void volume of 11.1% by volume and an ESCA value of 0.69.

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  • Organic Chemistry (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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JP01317699A JP4331813B2 (ja) 1998-06-25 1999-01-21 塩素化塩化ビニル系樹脂粒子の製造方法及びそれにより得られた樹脂粒子
JP11/013175 1999-01-21
JP1443099 1999-01-22
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US20090169785A1 (en) * 2006-04-11 2009-07-02 Saleem Shakir Heat tolerant, optically clear cpvc and method of making same
US20150094417A1 (en) * 2013-09-27 2015-04-02 G.B.D. Corp. Pipe joining material for connecting pipes
US20160008786A1 (en) * 2012-10-18 2016-01-14 Reliance Industries Limited Halogenation Of Hydrocarbons
WO2017155983A1 (fr) * 2016-03-08 2017-09-14 Oxy Vinyls, Lp Procédés de chloration de polychlorure de vinyle
CN108602911A (zh) * 2016-02-25 2018-09-28 株式会社钟化 氯化氯乙烯系树脂的制造方法
US11339233B2 (en) 2017-09-15 2022-05-24 Geon Performance Solutions, Llc Flame retardant poly(vinyl chloride) compounds
US11466103B2 (en) 2016-03-08 2022-10-11 Oxy Vinyls, Lp Methods for providing polyvinyl chloride particles for preparing chlorinated polyvinyl chloride
US11629204B2 (en) 2017-10-25 2023-04-18 Hanwha Solutions Corporation Method for preparing chlorinated polyvinyl chloride resin
US11739880B2 (en) 2021-05-19 2023-08-29 Samuel Gottfried High temperature protection wrap for plastic pipes and pipe appliances

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CN102558407B (zh) * 2012-02-17 2014-11-26 华东理工大学 一种氯化聚氯乙烯及其制备方法和应用
KR20190079740A (ko) 2017-12-27 2019-07-08 (주)고비 불균일한 경계면을 가지는 합성수지 다중관

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KR100627122B1 (ko) 2006-09-22

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